Photosensitive composition and planographic printing plate using the same

ABSTRACT

The present invention provides a photosensitive composition comprising an infrared absorbing agent represented by the following formula (I) and a polymer compound which is insoluble in water and soluble in an aqueous alkali solution and becoming soluble in an aqueous alkali solution by radiation of an infrared laser. In the formula described below, R 1  and R 2  independently represent an alkyl group having 1 to 18 carbon atoms or an alkyl group having 9 to 30 carbon atoms and Z represents a heptamethine group which may have a substituent. The definitions of other substituents are shown in the specification. According to the present invention, a photosensitive composition having high development latitude and storage stability, together with a positive type planographic printing plate for direct plate-making which can form an image with high sensitivity by using an infrared laser, are provided.

BACKGROUND OF THE INVENTION

1. Field of Invention

The present invention relates to a photosensitive composition suitableas a positive type image recording material and to a planographicprinting plate using the photosensitive composition, and, particularly,to a photosensitive composition and a planographic printing plate usingthe same, the photosensitive composition being capable of forming apositive type image by using an infrared laser, the composition beingsuitable for a planographic printing plate for the so-called directplate-making which enables writing by the heat of an infrared laser,thermal head or the like and can be directly performed based on digitalsignals from a computer or the like.

2. Description of the Related Art

Along with recent development of a solid laser and semiconductor laseremitting light within a range from the near infrared region to theinfrared region, a system of effecting plate-making directly fromdigital data of a computer using these infrared lasers has beenremarked.

A positive type planographic printing plate (material) for directplate-making using an infrared laser is disclosed in Japanese PatentApplication Laid-Open (JP-A) No. 7-285275. This invention relates to animage recording material obtained by adding a material which absorbslight to generate heat and a positive type photosensitive compound suchas a quinone diazide compound to a resin which is soluble in an aqueousalkali solution. The positive photosensitive compound functions as andissolution-preventing agent, which substantially decreases thesolubility of the resin soluble in an aqueous alkali solution, in animage portion. In a non-image portion, on the other hand, thephotosensitive compound is decomposed by heat so that it does notdevelop dissolution-preventing ability, and can eventually be removed bydevelopment to thereby form an image.

It has been found as a result of the studies made by the inventors ofthe present invention that a positive image can be obtained even ifthese quinone azide compounds are not added to the image recordingmaterial. However, an image recording material from which these quinoneazide compounds are simply excluded has the drawback that the stabilityof sensitivity to the density of a developer, namely, developmentlatitude is impaired resultantly.

Meanwhile, onium salts and compounds which are insoluble in an alkaliand can have hydrogen-hydrogen bonding are known to have a significanteffect of preventing an alkali-soluble polymer from dissolving in analkali. As an image recording material which is adapted to an infraredlaser, compositions using a cationic infrared ray absorbing dye as anagent suppressing the dissolution of an aqueous alkali-solution-solublepolymer exhibit a positive effect as described in WO97/39894. Thispositive effect represents the effect of forming an image by making apolymer film of the layser-irradiated part lose thedissolution-suppressing ability, by making use of the heat generatedwhen an infrared ray absorbing dye absorbs laser light.

Its image recording properties is sufficient on the surface of aphotosensitive material irradiated with the laser. However, onlyinsufficient image recording properties is obtained in the deep portionof the photosensitive material due to thermal diffusion. Therefore, itis hard to provide ON-OFF of exposed portions/unexposed portions inconcerning alkali developing, posing the problem that a good image isnot obtained (i.e., low sensitivity, narrow development latitude). Thedevelopment latitude mentioned here indicates an allowable range inwhich a good image can be formed when the alkali concentration of analkali developer is changed.

SUMMARY OF THE INVENTION

Accordingly an object of the present invention is to provide aphotosensitive composition which has a wide development latitude andhigh image recording properties and exhibits a high storage stability(that is, its image recording properties is not lowered even if it isstored for a long period of time) and to also provide a positive typeplanographic printing plate using the photosensitive composition, theprinting plate being capable of forming an image by using an infraredlaser used for direct plate-making.

The inventors of the present invention have made earnest studies for thepurpose of increasing image recording properties, namely, developmentlatitude and improving storage stability and as a result, found thatboth of the development latitude and the storage stability are improvedby using a specific infrared absorbing agent. The present invention wascompleted on the basis of this discovery.

According to a first aspect of the present invention, there is provideda photosensitive composition comprising an infrared absorbing agent (a)represented by the following formula (I) and a polymer compound (b)which is insoluble in water and soluble in an aqueous alkali solutionwherein the solubility of the photosensitive composition in an aqueousalkali solution is changed by radiation of an infrared laser.

wherein X¹ and X² independently represent —CR⁷R⁸—, —S—, —Se—, —NR⁹—,—CH═CH— or —O—, R¹ and R² independently represent an alkyl group having9 to 30 carbon atoms, R³, R⁴, R⁵ and R⁶ independently represent ahydrogen atom or an alkyl group having 1 to 10 carbon atoms and mayrepresent a plurality of atoms required for R³ and R⁴ or R⁵ and R⁶ to becombined with each other to form an aliphatic 5- or 6-membered ring, anaromatic 6-membered ring, an aromatic 10-membered ring, a substitutedaromatic 6-membered ring or a substituted aromatic 10-membered ring, R⁷and R⁸ independently represent an alkyl group having 1 to 18 carbonatoms or an aryl group having 6 to 18 carbon atoms, R⁹ represents analkyl group having 1 to 18 carbon atoms or an aryl group having 6 to 18carbon atoms, Z represents a heptamethine group which may have asubstituent wherein the substituent may be an alkyl group having 8 orless carbon atoms, a halogen atom or an amino group or the heptamethinegroup may include a cyclohexene ring or a cyclopentene ring which mayhave a substituent formed by combining substituents on two methinecarbons with each other where the substituent on the ring structure isselected from an alkyl group having 6 or less carbon atoms or a halogenatom and Q represents a counter ion.

According to a second aspect of the present invention, there is provideda photosensitive composition comprising an infrared absorbing agent (c)represented by the following formula (II) and a polymer compound (b)which is insoluble in water and soluble in an aqueous alkali solutionwherein the solubility of the photosensitive composition in an aqueousalkali solution is changed by radiation of an infrared laser.

wherein X¹ and X² independently represent —CR⁸R⁹—, —S—, —Se—, —NR¹⁰—,—CH═CH— or —O—, n denotes an integer of 2, 3 or 4, R¹ and R²independently represent an alkyl group having 1 to 18 carbon atoms or asubstituted alkyl group having 1 to 18 carbon atoms, R³ represents agroup selected from the group consisting of an alkyl group having 1 to10 carbon atoms, a substituted alkyl group having 1 to 10 carbon atoms,an aryl group, a substituted aryl group and a heterocyclic group having5 to 6 carbon atoms in the ring, R⁴, R⁵, R⁶ and R⁷ independentlyrepresent a hydrogen atom, an alkyl group having 1 to 10 carbon atoms ora substituted alkyl group having 1 to 10 carbon atoms and may representa plurality of atoms required for R⁴ and R⁵ or R⁶ and R⁷ to be combinedwith each other to form an aliphatic 5- or 6-membered ring, an aromatic6-membered ring, an aromatic 10-membered ring, a substituted aromatic6-membered ring or a substituted aromatic 10-membered ring, R⁸ and R⁹independently represent an alkyl group having 1 to 18 carbon atoms, asubstituted alkyl group having 1 to 18 carbon atoms, an aryl grouphaving 6 to 18 carbon atoms or a substituted aryl group having 6 to 18carbon atoms, R¹⁰ represents an alkyl group having 1 to 18 carbon atoms,a substituted alkyl group having 1 to 18 carbon atoms, an aryl grouphaving 6 to 18 carbon atoms or a substituted aryl group having 6 to 18carbon atoms and Q represents a counter ion having a molecular weight of70 or more.

According to a third aspect of the present invention, the counter ion Qof the infrared absorbing agent represented by the formula (I) or (II)is preferably a counter ion represented by the following formula (III)or containing a sulfonic acid structure.

wherein A represents an atom selected from the group consisting of B, P,As, Sb, Cl and Br, Y represents a halogen atom or an oxygen atom and mdenotes an integer from 1 to 6.

The action of each of the above inventions are not clear, however, as tothe invention according to the first aspect, a long chain alkyl group isintroduced at the N position of a dye in the infrared absorbing agent(a) represented by the formula (I), whereby the organicity of the dye isimproved and efficient conversion from light to heat on the surface ofthe photosensitive layer is carried out. Also, the presence of theinfrared absorbing agent having a long chain alkyl group improves thestability in storage. Consequently, the infrared absorbing agent (a) isimproved in the affinity to the aqueous alkali(solution)-soluble polymer(b) and in the ability of suppressing the dissolution of the aqueousalkali-soluble polymer (b). It is considered that, due to such reasons,an improvement in image recording properties and a suppression effect ofthe deterioration of image recording properties after long term storagecan be effected.

As to the invention according to the second aspect, a —S—interconnectingsubstituent is introduced on the methine chain of the dye in theinfrared absorbing agent (c) represented by the formula (II), wherebythe organicity of the dye is improved. Consequently, the infraredabsorbing agent (c) is improved in the affinity to the aqueousalkali-soluble polymer (b) and in the ability of suppressing thedissolution of the aqueous alkali-soluble polymer (b). It is thereforeconsidered that, due to such reasons, an improvement in image recordingproperties and a suppression effect of the deterioration of imagerecording properties after long term storage can be effected.

In the infrared absorbing agent (c) used in the invention according tothe second aspect, a counter anion Q having a molecular weight of 70 ormore is used. When the molecular weight of the counter ion is small, anacid derived from a counter anion produced by the decomposition of thedye is volatized, which tends to cause such disadvantages that theinfrared absorbing agent becomes unstable, the organicity of the wholeinfrared absorbing agent is decreased and hence the affinity of theinfrared absorbing agent to the aqueous alkali-soluble polymer (b) isdecreased, resulting in that the dye tends to coagulate. However, when acounter anion having a molecular weight of 70 or more is used in thesame manner as in the present invention, the organicity of the dye canbe made high and further the stability of the infrared absorbing agentis improved. It is therefore considered that the deterioration of imagerecording properties after long term storage can be suppressed.

According to a fourth aspect of the present invention, there is provideda planographic printing plate comprising a photosensitive layerconsisting of the aforementioned photosensitive composition, thephotosensitive layer being disposed on a substrate.

DESCRIPTION OF THE PREFERRED EMBODIMENTS First Embodiment

The first embodiment of the present invention will be described indetail below. [Infrared absorbing agent (a) represented by the generalformula (I)]

In the infrared absorbing agent (c) used in the invention according tothe second aspect, a counter anion Q having a molecular weight of 70 ormore is used. When the molecular weight of the counter ion is small, anacid derived from a counter anion produced by the decomposition of thedye is volatilized, which tends to cause such disadvantages that theinfrared absorbing agent becomes unstable, the organicity of the wholeinfrared absorbing agent is decreased and hence the affinity of theinfrared absorbing agent to the aqueous alkali-soluble polymer (b) isdecreased, resulting in that the dye tends to coagulate. However, when acounter anion having a molecular weight of 70 or more is used in thesame manner as in the present invention, the organicity of the dye canbe made high and further the stability of the infrared absorbing agentis improved. It is therefore considered that the deterioration of imagerecording properties after long term storage can be suppressed.

The above mentioned infrared absorbing agent represented by the generalformula (I) will be described further in detail.

In the general formula (I), each of X¹ and X² independently represents—CR⁷R⁸—, —S—, —Se—, —NR⁹—, —CH═CH— or —O—. Wherein, R⁷ and R⁸ representan alkyl group having 1 to 18 carbon atoms, a substituted alkyl grouphaving 1 to 18 carbon atoms, an aryl group having 6 to 18 carbon atoms,or a substituted aryl group having 6 to 18 carbon atoms.

Each of R¹ and R² independently represents an alkyl group having 9 to 30carbon atoms, and these alkyl groups may have a substituent.

Each of R³, R⁴, R⁵ and R⁶ independently represents a hydrogen atom, analkyl group having 1 to 10 carbon atoms or a substituted alkyl grouphaving 1 to 10 carbon atoms, R³ and R⁴ or R⁵ and R⁶ may be bondedtogether and represent a plurality of atoms necessary for forming analiphatic 5-membered or 6-membered ring, aromatic 6-membered ring,aromatic 10-membered ring, substituted aromatic 6-membered ring orsubstituted aromatic 10-membered ring. R⁹ represents an alkyl grouphaving 1 to 18 carbon atoms, a substituted alkyl group having 1 to 18carbon atoms, an aryl group having 6 to 18 carbon atoms, or asubstituted aryl group having 6 to 18 carbon atoms.

The above-mentioned alkyl group represented by R¹ to R⁹ includesstraight chain, branched or cyclic alkyl groups having 9 to 30, or 1 to18 carbon atoms. Specific examples thereof include a methyl group, ethylgroup, propyl group, butyl group, pentyl group, hexyl group, heptylgroup, octyl group, nonyl group, decyl group, undecyl group, dodecylgroup, tridecyl group, hexadecyl group, octadecyl group, eicosyl group,isopropyl group, isobutyl group, s-butyl group, t-butyl group, isopentylgroup, neopentyl group, 1-methylbutyl group, isohexyl group,2-ethylhexyl group, 2-methylhexyl group, cyclohexyl group, cyclopentylgroup and 2-norbornyl group. Among them, it is more preferable that R¹and R² represent a straight chain alkyl group, R³ to R⁹ represent astraight chain alkyl group having 1 to 10 carbon atoms, a branched alkylgroup having 3 to 12 carbon atoms or a cyclic alkyl group having 5 to 10carbon atoms.

When these alkyl groups have a substituent, monovalent non-metal atomsexcepting hydrogen are used as the substituent. Preferable examplesthereof include halogen atoms (—F, —Br, —Cl, —I), hydroxyl group, alkoxygroups, aryloxy groups, mercapto group, alkylthio groups, arylthiogroups, alkyldithio groups, aryldithio groups, amino group, N-alkylaminogroups, N,N-dialkylaminogroups, N-arylaminogroup, N,N-diarylaminogroups,N-alkyl-N-arylaminogroups, acyloxygroups, carbamoyloxygroup,N-alkylcarbamoyloxy groups, N-arylcarbamoyloxy groups,N,N-dialkylcarbamoyloxy groups, N,N-diarylcarbamoyloxy groups,N-alkyl-N-arylcarbamoyloxy groups, alkylsulfoxy groups, arylsulfoxygroups, acylthio group, acylamino groups, N-alkylacylamino groups,N-arylacylamino groups, ureido group, N′-alkylureido groups,N′,N′-dialkylureido groups, N′-arylureido groups, N′,N′-diarylureidogroups, N′-alkyl-N′-arylureido groups, N-alkylureido groups,N-arylureido groups, N′-alkyl-N-alkylureido groups,N′-alkyl-N-arylureido groups, N′,N′-dialkyl-N-alkylureido groups,N′,N′-dialkyl-N-arylureido groups, N′-aryl-N-alkylureido groups,N′-aryl-N-arylureido groups, N′,N′-diaryl-N-alkylureido groups,N′,N′-diaryl-N-arylureido groups, N′-alkyl-N′-aryl-N-alkylureido groups,N′-alkyl-N′-aryl-N-arylureido groups, alkoxycarbonylamino groups,aryloxycarbonylamino groups, N-alkyl-N-alkoxycarbonylamino groups,N-alkyl-N-aryloxycarbonylamino groups, N-aryl-N-alkoxycarbonylaminogroups, N-aryl-N-aryloxycarbonylamino groups, formyl group, acyl groups,carboxyl group and conjugated base group (hereinafter, referred to as“carboxylate”), alkoxycarbonyl groups, aryloxycarbonyl groups, carbamoylgroups, N-alkylcarbamoyl groups, N,N-dialkylcarbamoyl groups,N-arylcarbamoyl groups, N,N-diarylcarbamoyl groups,N-alkyl-N-arylcarbamoyl groups, alkylsulfinyl groups, arylsulfinylgroups, alkylsulfonyl group, arylsulfonyl groups, sulfo group (—SO₃H)and conjugated base thereof (hereinafter, referred to as “sulfonatogroup”), alkoxysulofnyl groups, aryloxysulfonyl groups, sulfinamoylgroup, N-alkylsulfinamoyl groups, N,N-dialkylsulfinamoyl groups,N-arylsulfinamoyl groups, N,N-diarylsulfinamoyl groups,N-alkyl-N-arylsulfinamoyl groups, sulfamoyl group, N-alkylsulfamonylgroups, N,N-dialkylsulfamoyl groups, N-arylsulfamoyl groups,N,N-diarylsulfamoyl groups, N-alkyl-N-arylsulfamoyl groups,N-acylsulfarnoyl group and conjugated base group,N-alkylsulfonylsulfamoyl groups (—SO₂NHSO₂R, R represents an alkylgroup) and conjugated base group thereof, N-arylsulfonylsulfamoyl groups(—SO₂NHSO₂Ar, Ar represents a aryl group) and conjugated base groupthereof, N-alkylsulfonylcarbamoyl groups (—CONHSO₂R, R represents analkyl group) and conjugated base group thereof, N-arylsulfonylcarbamoylgroups (—CONHSO₂Ar, Ar represents an aryl group) and conjugated basegroup thereof, alkoxysilyl groups (—SI(OR)₃, R represents an alkylgroup), aryloxysilyl groups (—SI(OAr)₃, Ar represents an aryl group),hydroxysilyl group (—Si(OH)3) and conjugated base group thereof,phosphono group (—PO₃H₂) and conjugated base group thereof (hereinafter,referred to as “phosphonato group”), dialkylphosphono group (—PO₃R², Rrepresents an alkyl group), diarylphosphono group (—PO₃Ar₂, Arrepresents an aryl group), alkylarylphosphono group (—PO₃(R)(Ar), Rrepresents an alkyl group and Ar represents an aryl group),monoalkylphosphono group (—PO3H(R), R represents an alkyl group) andconjugated base group thereof (hereinafter, referred to as“alkylphosphonato group”), monoarylphosphono group (—PO₃H(Ar), Arrepresents an aryl group) and conjugated base group thereof(hereinafter, referred to as “arylphosphonato group”), phosphonooxygroup (—OPO₃H₂) and conjugated base group thereof (hereinafter, referredto as “phosphonatooxy group”), dialkylphosphonooxy group (—OPO₃(R)₂ Rrepresents an alkyl group), diarylphosphonooxy group (—OPO₃(Ar)₂ Arrepresents an aryl group), alkylarylphosphonooxy group (—OPO₃(R)(Ar), Rrepresents an alkyl group and Ar represents an aryl group),monoalkylphosphonooxy group (—OPO₃H(R), R represents an alkyl group) andconjugated base group thereof (hereinafter, referred to as“alkylphosphonatooxy group”), monoarylphosphonooxy group (—OPO₃H(Ar), Arrepresents an aryl group) and conjugated base group thereof(hereinafter, referred to as “arylphosphonatooxy group”), cyano group,nitro group, aryl groups, alkenyl group and alkinyl groups.

As specific examples of the alkyl group in these substituents to besubstituted on alkyl groups, the above-mentioned alkyl groups are listedlikewise, and specific examples of the aryl group include a phenylgroup, biphenyl group, naphthyl group, tolyl group, xylyl group, mesitylgroup, cumenyl group, fluorophenyl group, chlorophenyl group,bromophenyl group, chloromethylphenyl group, hydroxyphenyl group,methoxyphenyl group, ethoxyphenyl group, phenoxyphenyl group,acetoxyphenyl group, benzoyloxyphenyl group, methylthiophenyl group,phenylthiophenyl group, methylaminophenyl group, dimethylaminophenylgroup, acetylaminophenyl group, carboxyphenyl group,methoxycarbonylphenyl group, ethoxycarbonylphenyl group,phenoxycarbonylphenyl group, N-phenylcarbamoylphenyl group, phenylgroup, nitrophenyl group, cyanophenyl group, sulfophenyl group,sulfonatophenyl group, phosphonophenyl group, phosphonatophenyl groupand the like.

As the substituent, aryl group to be substituted on alkyl groups, theabove-exemplified aryl groups are listed likewise, and examples of thealkenyl group include a vinyl group, 1-propenyl group, 1-butenyl group,cinnamyl group, 2-chloro-1-ethenyl group and the like, and examples ofthe alkyl group include an ethinyl group, 1-propinyl group, 1-butinylgroup, trimethylsilylethinyl group, phenylethinyl group and the like

Of these substituents, more preferable examples thereof include halogenatoms (—F, —Br, —Cl, —I), alkoxy groups, aryloxy groups, alkylthiogroups, arylthio groups, N-alkylamino groups, N,N-dialkylamino groups,acyloxy groups, N-alkylcarbamoyloxy groups, N-arylcarbamoyloxy groups,acylamino groups, formyl group, carboxyl group, alkoxycarbonyl groups,aryloxycarbonyl groups, carbamoyl group, N-alkylcarbamoyl groups,N,N-dialkylcarbamoyl groups, N-arylcarbamoyl groups,N-alkyl-N-arylcarbamoyl groups, sulfo group, sulfonato group, sulfamoylgroup, N-alkylsulfamoyl groups, N,N-dialkylsulfamoyl groups,N-arylsulfamoyl groups, N-alkyl-N-arylsulfamoyl group, phosphono group,phosphonato group, dialkylphosphono groups, diarylphosphono groups,monoalkyl phosphono groups, alkylphosphonato groups, monoarylphosphonogroups, arylphosphonato groups, phosphonooxy group, phosphonatooxygroup, aryl groups, alkenyl groups and the like.

On the other hand, in substituted alkyl groups, as the alkylene groupwhich is combined with a substituent to form a substituted alkyl group,divalent organic residues obtained by deleting any one hydrogen atom onthe above-mentioned alkyl groups having 1 to 30 carbon atoms are listed,and preferable examples of R³ to R⁹ include straight chain alkylenegroups having 1 to 12 carbon atoms, branched alkylene groups having 3 to12 carbon atoms and cyclic alkylene groups having 5 to 10 carbon atoms.Preferable specific examples of the substituted alkyl group obtained bycombining the above-mentioned substituent with an alkylene group includechloromethyl group, bromomethyl group, 2-chloroethyl group,trifluoromethyl group, methoxymethyl group, methoxyethoxyethyl group,allyloxymethyl group, phenoxymethyl group, methylthiomethyl group,tolylthiomethyl group, ethylaminoethyl group, diethylaminopropyl group,morpholinopropyl group, acetyloxymethyl group, benzoyloxymethyl group,N-cyclohexylcarbamoyloxyethyl group, N-phenylcarbamoyloxyethyl group,acetylaminoethyl group, N-methylbenzoylaminopropyl group, 2-oxoethylgroup, 2-oxopropyl group, carboxypropyl group, methoxycarbonylethylgroup, methoxycarbonylmethyl group, methoxycarbonylbutyl group,allyloxycarbonylbutyl group, chlorophenoxycarbonylmethyl group,carbamoylmethyl group, n-methylcarbamoylethyl group,N,N-dipropylcarbamoylmethyl group, N-(methoxyphenyl)carbamoylethylgroup, N-methyl-N-(sulfonyl)carbamoylmethyl group, sulfopropyl group,sulfobutyl group, sulfonatobutyl group, sulfamoylbutyl group,N-ethylsulfamoylmethyl group, N,N-dipropylsulfamoylpropyl group,N-tolylsulfamoylpropyl group, N-methyl-N-(phosphonophenyl)sulfamoyloctyl group, phosphonobutyl group, phosphonatohexyl group,diethylphosphonobutyl group, diphenylphosphonopropyl group,methylphosphonobutyl group, methylphosphonatobutyl group,tolylphosphonohexyl group, tolylphosphonatohexyl group,phosphonooxypropyl group, phosphonooxybutyl group, benzyl group,phenethyl group, α-methylbenzyl group, 1-methyl-1-phenylethyl group,p-methylbenzyl group, cinnamyl group, allyl group, 1-propenylmethylgroup, 2-butenyl group, 2-methylallyl group, 2-methylpropenylmethylgroup, 2-propinyl group, 2-butinyl group, 3-butinyl group and the like.

As the above-mentioned aryl group represented by R¹ to R¹⁰, those inwhich one to three benzene rings form a condensed ring and those inwhich a benzene ring and a 5-membered unsaturated ring form a condensedring are listed, and specific examples thereof include a phenyl group,naphthyl group, anthryl group, phenanthryl group, indenyl group,acenabutenyl group and fluorenyl group, and of these groups, a phenylgroup and naphthyl group are more preferable.

As the substituted aryl group, those having as a substituent amonovalent non-metal atom excepting hydrogen on a ring forming carbonatom of the above-mentioned aryl groups are used. As the preferableexample of the substituent, the above-mentioned alkyl groups,substituted alkyl groups, and those exemplified as a subs tituent onsubstituted alkyl groups, are listed.

Preferable specific examples of such a substituted aryl group include abiphenyl group, tolyl group, xylyl group, mesityl group, cumenyl group,chlorophenyl group, bromophenyl group, fluorophenyl group,chloromethylphenyl group, trifluoromethylphenyl group, hydroxyphenylgroup, methoxyphenyl group, methoxyethoxyphenyl group, allyloxyphenylgroup, phenoxyphenyl group, methylthiophenyl group, tolylthiophenylgroup, phenylthiophenyl group, ethylaminophenyl group,dimethylaminophenyl group, diethylaminophenyl group, morpholinophenylgroup, acetyloxyphenyl group, benzoyloxyphenyl group,N-cyclohexylcarbamoyloxyphenyl group, N-phenylcarbamoyloxyphenyl group,acetylaminophenyl group, N-methylbenzoylaminophenyl group, carboxyphenylgroup, methoxycarbonylphenyl group, allyloxycarbonylphenyl group,chlorophenoxycarbonylphenyl group, carbamoylphenyl group,N-methylcarbamoylphenyl group, N,N-dipropylcarbamoylphenyl group,N-(methoxyphenyl)carbamoylphenyl group,N-methyl-N-(sulfenyl)carbamoylphenyl group, sulfenyl group,sulfonatophenyl group, sulfamoylphenyl group, N-ethylsulfamoylphenylgroup, N,N-dipropylsulfamoylphenyl group, N-tolylsulfamoylphenyl group,N-methyl-N-(phosphonophenyl)sulfamoylphenyl group, phosphonophenylgroup, phosphonatophenyl group, diethylphosphonophenyl group,diphenylphosphonophenyl group, methylphosphonophenyl group,methylphosphonatophenyl group, tolylphosphonophenyl group,tolylphosphonatophenyl group, allylphenyl group, 1-propenylmethylphenylgroup, 2-butenylphenyl group, 2-methylallylphenyl group,2-methylpropenylphenyl group, 2-propinylphenyl group, 2-butinylphenylgroup, 3-butinylphenyl group and the like.

Z represents a heptamethine group which may have a substituent. When aheptamethine group has a substituent, examples of the substituentinclude alkyl groups having 8 or less carbon atoms, halogen atoms,alkoxy groups, aryloxy groups, alkylthio groups, arylthio groups,N-alkylamino groups, N,N-dialkylamino groups, N-arylamino groups,N,N-diarylamino groups, hetero cyclic groups and the like, and thesesubstituents may be further substituted with the same substituents asexemplified to R¹ to R⁶.

Among them, from the standpoints of absorption wavelength suitability asan infrared absorbing agent and easiness of synthesis thereof,preferable are a heptamethine group having no substituent, aheptamethine group having a halogen atom as a substituent, aheptamethine group having arylthio group as a substituent, aheptamethine group having N,N-diarylamino group as a substituent, andthe like.

This heptamethine group may be one containing a cyclohexene ring orcyclopentene ring formed by mutual connection of substituents on twomethane carbons. One or more ring structures as described above may bepresent in heptamethine. These ring structures may have a substituent,and as the substituent on this ring structure, alkyl groups having 6 orless carbon atoms and halogen atoms are listed. Among them, alkyl groupshaving 6 or less carbon atoms and the like are preferable from thestandpoint of easiness of synthesis.

Q represents a counter ion, and may form a bond with R¹ to R⁶ to give anintramolecular salt. This counter ion Q is not particularly limited, andany ion known as a counter ion of a known infrared absorption colorantcan be applied providing it is suitable for absorption wavelength rangeof an infrared absorbing agent.

As this counter ion, those represented by the above-mentioned generalformula (II) are preferable, and in the formula, A represents an atomselected from the group consisting of B, P, As, Sb, Cl and Br, and B, P,Sb and Cl are preferable from the standpoints of easiness of synthesisand safety of a compound.

Y represents a halogen atom, for example, Cl, I, Br, F and the like oran oxygen atom. Among them, Y preferably represents a fluorine or oxygenatom from the standpoint of easiness in raw material availability.

m represents an integer of 1 to 6, and preferably in the range from 4 to6.

Preferable counter ions Q in this embodiment will be listed below, but Qis not restricted to them.

As Q, those having a sulfonic acid structure in the structure are alsopreferably used.

Examples of the counter anion having a sulfonic acid structure which canbe used as a counter ion Q in an infrared absorbing agent in thisembodiment include the following ions.

1) methanesulfonate ion,

2) ethanesulfonate ion,

3) 1-propanesulfonate ion,

4) 2-propanesulfonate ion,

5) n-butanesulfonate ion,

6) allylsulfonate ion,

7) 10-camphorsulfonate ion,

8) trifluoromethanesulfonate ion,

9) pentafluoroethanesulfonate ion,

10) benzenesulfonate ion,

11) p-toluenesulfonate ion,

12) 3-methoxybenzenesulfonate ion,

13) 4-methoxybenzenesulfonate ion,

14) 4-hydroxybenzenesulfonate ion,

15) 4-chlorobenzenesulfonate ion,

16) 3-nitrobenzenesulfonate ion,

17) 4-nitrobenzenesulfonate ion,

18) 4-acetylbenzenesulfonate ion,

19) pentafluorobenzenesulfonate ion,

20) 4-dodecylbenzenesulfonate ion,

21) mesitylenesulfonate ion,

22) 2,4,6-triisopropylbenzenesulfonate ion,

23) 2-hydroxy-4-methoxybenzophenone-5-sulfonate ion,

24) dimethyl isophthalate-5-sulfonate ion,

25) diphenylamine-4-sulfonate ion,

26) 1-naphthalenesulfonate ion,

27) 2-naphthalenesulfonate ion,

28) 2-naphthol-6-sulfonate ion,

29) 2-naphthol-7-sulfonate ion,

30) anthraquinone-1-sulfonate ion,

31) anthraquinone-2-sulfonate ion,

32) 9,10-dimethoxyanthracene-2-sulfonate ion,

33) 9,10-diethoxyanthracene-2-sulfonate ion,

34) quinoline-8-sulfonate ion,

35) 8-hydroxyquinoline-5-sulfonate ion,

36) 8-anilino-naphthalene-1-sulfonate ion.

A method for producing an infrared absorbing agent represented by thegeneral formula (I) will be described below.

The infrared absorbing agent represented by the general formula (I) canbe produced by a known organic synthesis technology. As specificsynthesis methods, there are listed methods described in U.S. Pat. No.5,441,866, Zh. Org. Khim. vol. 28, (No. 10), 1992, pp. 2159 to 2164, EUPatent No. 464,543, A1.

Specific examples [(IR-1) to (IR-30)] of the infrared absorbing agentrepresented by the general formula (I) are listed below, but do notlimit the scope of the infrared absorbing agent of this embodiment.

In the present embodiment, the above-mentioned infrared absorbing agentcan be added in an amount of 0.01 to 50% by weight, preferably of 0.1 to20% by weight, more preferably of 0.5 to 15% by weight based on thetotal solid amount of a photosensitive composition. If the additionamount is less than 0.01% by weight, an image can not be formed by thisphotosensitive composition, and if added in an amount of over 50% byweight, there is a fear of generation of stains on non-image portionswhen the composition used in a photosensitive layer of a planographicprinting plate.

In a photosensitive composition of this embodiment, other pigment or dyehaving infrared ray absorbing properties can be added for the purpose ofimproving image forming properties, in addition to the above-mentionedinfrared absorbing agent.

As the pigment, there can be used commercially available pigment andthose described in Color Index (C. I.) manual, “Saishin Ganryo Binran(current pigment manual)” (Nippon Ganryo Gijutsu Kyokai, 1977), “SaishinGanryo Oyo Gijutsu (current pigment application technology)” (CMC,1986), “Insatsu Ink Gijutsu (printing ink technology)” (CMC, 1984).

As the pigment, black pigments, yellow pigments, orange pigments, brownpigments, red pigments, violet pigments, blue pigments, green pigments,fluorescent pigments, metal powder pigments, and other polymer bondpigments are listed. Specifically, there can be used insoluble azopigments, azolake pigments, condensed azo pigments, chelate azopigments, phthalocyanine pigments, anthraquinone pigments, perylene andperynone pigments, thioindigo pigments, quinacridone pigments, dioxazinepigments, isoindolinone pigments, quinophthalone pigments, staining lakepigments, azine pigments, nitroso pigments, nitro pigments, naturalpigments, fluorescent pigments, inorganic pigments, carbon black and thelike.

These pigments may or may not be subjected to surface treatment. As thesurface treatment method, there are envisaged a method in which a resinor wax is coated on the surface, a method in which a surfactant isadhered, a method in which a reactive substance (for example, a silanecoupling agent, epoxy compound, polyisocyanate and the like) is bondedto the surface of a pigment, and the like. The above-mentioned surfacetreatment methods are described in “Kinzoku Sekken no Seishitsu to Oyo(nature and application of metal soap)” (Sachi Publication), “InsatsuInk Gijutsu (printing ink technology)” (CMC, 1984), and “Saishin GanryoOyo Gijutsu (current pigment application technology)” (CMC, 1986).

The particle size of a pigment is preferably in the range from 0.01 μmto 10 μm, and further preferably in the range from 0.05 μm to 1 μm,particularly, in the range from 0.1 μm to 1 μm. If the particle size ofa pigment is less than 0.01 μm, stability of a dispersed material in aphotosensitive layer coating solution is not preferable, while if over10 μm, uniformity of a photosensitive layer deteriorates.

For dispersing a pigment, known dispersing technologies used inproducing an ink and toner and the like can be used. As the dispersingmachine, a supersonic dispersing apparatus, sandmill, attritor, pearlmill, super mill, ball mill, impeller, disperser, KD mill, colloid mill,dinatron, three-roll mill, press kneader and the like are listed. Thedetails are described in “Saishin Ganryo Oyo Gijutsu (current pigmentapplication technology)” (CMC, 1986).

As the dye, there can be used commercially available dyes and thosedescribed in literatures (for example, “Senryo Binran (pigment manual)”(Yuki Gosei Kagaku Kyokai, 1970)). Specific examples thereof include azodyes, metal complex salt azo dyes, pyrazolone azo dyes, anthraquinonedyes, phthalocyanine dyes, carbonium dyes, quinoneimine dyes, methinedyes, cyanine dyes, diimonium dyes, aminium dyes and the like.

In this embodiment, among these pigments or dyes, those absorbing aninfrared ray or near infrared ray are particularly preferable since theyare suitable for use of laser emitting an infrared ray or near infraredray.

As such a pigment absorbing an infrared ray or near infrared ray, carbonblack is suitably used. Further, examples of the pigment absorbing aninfrared ray or near infrared ray include cyanine dyes described in JP-ANos. 58-125246, 59-84356, 59-202829, 60-78787 and the like, methine dyesdescribed in JP-A Nos. 58-173696, 58-181690, 58-194595 and the like,naphthoquinone dyes described in JP-A Nos. 58-112793, 58-224793,59-48187, 59-73996, 60-52940, 60-63744 and the like, squarylium pigmentsdescribed in JP-A No. 58-112792 and the like, cyanine dyes described inGB Patent No. 434,875, dihydroperimidinesquarylium dyes described inU.S. Pat. No. 5,380,635, and the like.

Further, as the dye, near infrared absorption sensitizers described inU.S. Pat. No. 5,156,938 are also used suitably, and further, there areparticularly preferably used arylbenzo(thio)pyrylium salts described inU.S. Pat. No. 3,881,924, trimethine thiopyrylium salts described in JP-ANo. 57-142645 (U.S. Pat. No. 4,327,169), pyrylium-based compoundsdescribed in JP-A Nos. 58-181051, 58-220143, 59-41363, 59-84248,59-84249, 59-146063 and 59-146061, cyanine pigments described in JP-ANo. 59-216146, pentamethine thiopyrylium salts described in U.S. Pat.No. 4,283,475, and pyrylium compounds disclosed in Japanese PatentApplication Publication (JP-B) Nos. 5-13514 and 5-19702 and the like,and Epolight III-178, Epolight III-130, Epolight III-125, EpolightIV-62A (manufactured by Eporin) and the like as commercially availableproducts.

As particularly preferable other examples of the dye, near infraredabsorbing dyes represented by the formula (I) and (II) in U.S. Pat. No.4,756,993 are listed.

The pigments or dyes can be added in an amount of 0.01 to 50% by weight,preferably of 0.1 to 10% by weight, and in the case of a dye,particularly preferably of 0.5 to 10% by weight and in the case of apigment, particularly preferably of 3.1 to 10% by weight based on thetotal solid content of a printing plate material. When the additionamount of the pigment or dye is less than 0.01% by weight, sensitivitydecreases, while when over 50% by weight, uniformity of a photosensitivelayer is lost and durability of a recorded layer deteriorates.

These dyes or pigments may be added to a photosensitive composition andadded together with other components to a photosensitive layer, andalternatively, in producing a planographic printing plate, a layer otherthan a photosensitive layer may be provided to which the dyes orpigments are added. These dyes or pigments may be added alone or inadmixture of two or more.

[(b) Aqueous Alkali Solution-soluble Resin]

(b) An aqueous alkali solution-soluble polymer compound used in thepresent embodiment is a compound having an acid group structuredescribed below on the backbone chain or side chain of the polymercompound.

Phenolic hydroxyl group (—Ar—OH), carboxyl group (—CO₂H), sulfonategroup (—SO₃H), phosphate group (—OPO₃H), sulfoneamide group (—SO₂NH—R),substituted sulfoneamide-based acid group (active imide group)(—SO₂NHCOR, —SO₂NHSO₂R, —CONHSO₂R).

Wherein, Ar represents a divalent aryl group which may have asubstituent, and R represents a hydrocarbon group which may have asubstituent.

Among these examples, (b-1) phenolic hydroxyl group, (b-2) sulfoneamidegroup, (b-3) active imide group are listed as a preferable acid group,and an aqueous alkali solution-soluble resin having (b-1) a phenolichydroxyl group (hereinafter, referred to as “resin having a phenolichydroxyl group”) can be used most preferably.

Examples of a polymer compound having (b-1) a phenolic hydroxyl groupinclude novolak resin such as polycondensates of phenol and formaldehyde(hereinafter, referred to as “phenolformaldehyde resin”),polycondensates of m-cresol and formaldehyde (hereinafter, referred toas “m-cresolformaldehyde resin”), polycondensates of p-cresol andformaldehyde, polycondensates of m-/p-mixed cresol and formaldehyde,polycondensates of phenol and cresol (any of m-, p-, or m-/p-mixture)and formaldehyde, and the like, and polycondensates of pyrogallol andacetone. Alternatively, copolymers obtained by copolymerizing monomershaving a phenol group on the side chain can also be used. As suchmonomers having a phenol group, acrylamide, methacrylamide, acrylate,methacrylate or hydroxystyrene having a phenol group are listed.Specifically, there can be suitably used N-(2-hydroxyphenyl)acrylamide,N-(3-hydroxyphenyl)acrylamide, N-(4-hydroxyphenyl)acrylamide,N-(2-hydroxyphenyl)acrylamide, N-(2-hydroxyphenyl)methacrylamide,N-(3-hydroxyphenyl)methacrylamide, N-(4-hydroxyphenyl)methacrylamide,o-hydroxyphenyl acrylate, m-hydroxyphenyl acrylate, p-hydroxyphenylacrylate, o-hydroxyphenyl methacrylate, m-hydroxyphenyl methacrylate,p-hydroxyphenyl methacrylate, o-hydroxystyrene, m-hydroxystyrene,p-hydroxystyrene, 2-(2-hydroxyphenyl)ethyl acrylate,2-(3-hydroxyphenyl)ethyl acrylate, 2-(4-hydroxyphenyl)ethyl acrylate,2-(2-hydroxyphenyl)ethyl methacrylate, 2-(3-hydroxyphenyl)ethylmethacrylate, 2-(4-hydroxyphenyl) ethyl methacrylate,2-(N′-(4-hydroxyphenyl)ureido)ethyl acrylate,2-(N′-(4-hydroxyphenyl)ureido)ethyl methacrylate and the like.

Polymers having a weight average molecular weight of 5.0×10² to 2.0×10⁵and a number average molecular weight of 2.0×10² to 1.0×10⁵ arepreferable from the standpoint of image forming ability. These resinsmay be used alone or in combination of two or more. When used incombination, there may be simultaneously used polycondensates offormaldehyde with phenol having as a substituent an alkyl group having 3to 8 carbon atoms such as a polycondensate of t-butylphenol withformaldehyde, and polycondensated of octylphenol with formaldehyde, asdescribed in U.S. Pat. No. 4,123,279.

Further, as described in U.S. Pat. No. 4,123,279, there may also besimultaneously used polycondensates of formaldehyde with phenol havingas a substituent an alkyl group having 3 to 8 carbon atoms such as at-butylphenolformaldehyde resin, octylphenolformaldehyde resin. Suchresins having a phenolic hydroxyl group may be used alone or incombination of two or more.

In the case of an aqueous alkali solution-soluble polymer compoundhaving (b-2) a sulfone amide group, as the monomer having (b-2) asulfone amide group, which is the main monomer constituting this polymercompound, there are listed monomers composed of a lower molecular weightcompound having one or more sulfoneamide groups in which at least onehydrogen atom is bonded at a nitrogen atom and one ore morepolymerizable unsaturated bonds, in one molecule. Among them, lowermolecular weight compounds having an acryloyl group, allyl group orvinyloxy group, and a substituted or mono-substituted aminosulfonylgroup or substituted sulfonylimino group are preferable.

Examples of these compound include the following compounds representedby the general formulae (4) to (8) described below.

In the general formulae, each of X¹ and X² independently represents —O—or —NR¹⁷—. Each of R²¹ and R²⁴ independently represents a hydrogen atomor —CH₃. Each of R²², R²⁵, R²⁹, R³² and R³⁶ independently represents analkylene group having 1 to 12 carbon atoms, cycloalkylene group, arylenegroup or aralkylene group, which may have a substituent. Each of R²³,R¹⁷ and R³³ independently represents a hydrogen atom, an alkyl grouphaving 1 to 12 carbon atoms, cycloalkyl group, aryl group or aralkylgroup, which may have a substituent. Each of R²⁶ and R³⁷ independentlyrepresents an alkyl group having 1 to 12 carbon atoms, cycloalkyl group,aryl group or aralkyl group, which may have a substituent. Each of R²⁸,R³⁰ and R³⁴ independently represents a hydrogen atom or —CH₃. Each ofR³¹ and R³⁵ independently represents a single bond, or an alkylene grouphaving 1 to 12 carbon atoms, cycloalkylene group, arylene group oraralkylene group, which may have a substituent. Each of Y¹ and Y²independently represents a single bond or —CO—.

Specifically, m-aminosulfonylphenyl methacrylate,N-(p-aminosulfonylphenyl) methacrylamide,N-(p-aminosulfonylphenyl)acrylamide and the like can be suitably used.

In the case of an aqueous alkali solution-soluble polymer compoundhaving (b-3) an active imide group, as the monomer having (b-3) anactive imide group, which has in the molecule an active imide grouprepresented by the following formula and which is the main monomerconstituting this polymer compound, there are listed monomers composedof a lower molecular weight compound having one or more active iminogroups represented by the following formula and one ore morepolymerizable unsaturated bonds, in one molecule.

As these compounds, there can be suitably usedN-(p-toluenesulfonyl)methacrylamide, N-(p-toluenesulfonyl) acrylamideand the like, specifically.

In the aqueous alkali solution-soluble copolymer which can be used inthe present embodiment, the monomer containing acidic groups of (b-1) to(b-3) is not necessarily restricted to one kind, two or more monomershaving the same acidic group or two or more monomers having differentacidic groups may be copolymerized.

As the copolymerization method, a graft copolymerization method, blockcopolymerization method, random copolymerization method and the likeconventionally known can be used.

The above-mentioned copolymer contains, as a copolymerization component,monomers having an acidic group (b-1) to (b-3) to be copolymerized in anamount preferably of 10 mol % or more, and more preferably of 20 mol %or more. When the amount of the copolymerization component is less than10 mol %, mutual action with a resin having a phenolic hydroxyl groupbecome insufficient, and an effect of improving development latitudewhich is a merit when the copolymer component is used becomesinsufficient.

Further, this copolymer may contain other copolymerization componentsthan the above-mentioned monomer containing an acidic group (b-1) to(b-3).

As the monomer which can be used as a copolymerization component, thefollowing monomers (1) to (12) can be used.

(1) Acrylates and methacrylates having and aliphatic hydroxyl group suchas, for example, a 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylateor the like.

(2) Alkyl acrylates such as methyl acrylate, ethyl acrylate, propylacrylate, butyl acrylate, amyl acrylate, hexyl acrylate, octyl acrylate,benzyl acrylate, 2-chloroethyl acrylate, glycidyl acrylate,N-dimethylaminoethyl acrylate and the like.

(3) Alkyl methacrylates such as methyl methacrylate, ethyl methacrylate,propyl methacrylate, butyl methacrylate, amyl methacrylate, hexylmethacrylate, cyclohexyl methacrylate, benzyl methacrylate,2-chloroethyl methacrylate, glycidyl methacrylate, N-dimethylaminoethylmethacrylate and the like.

(4) Acrylamides or methacrylamides such as acrylamide, methacrylamide,N-methylolacrylamide, N-ethylacrylamide, N-hexylmethacrylamide,N-cyclohexylacrylamide, N-hydroxyethylacrylamide, N-phenylacrylamide,N-nitrophenylacrylamide, N-ethyl-N-phenylacrylamide and the like.

(5) Vinyl ethers such as ethyl vinyl ether, 2-chloroethyl vinyl ether,hydroxyethyl vinyl ether, propyl vinyl ether, butyl vinyl ether, octylvinyl ether, phenyl vinyl ether and the like.

(6) Vinyl esters such as vinyl acetate, vinylchloro acetate,vinylbutyrate, vinyl benzoate and the like.

(7) Styrenes such as styrene, α-methylstyrene, methylstyrene,chloromethylstyrene and the like.

(8) Vinyl ketones such as methyl vinyl ketone, ethyl vinyl ketone,propyl vinyl ketone, phenyl vinyl ketone and the like.

(9) Olefins such as ethylene, propylene, isobutylene, butadiene,isoprene and the like.

(10) N-vinylpyrrolidone, N-vinylcarbazole, 4-vinylpyridine,acrylonitrile, methacrylonitrile and the like.

(11) Unsaturated imides such as Maleimide, N-acryloylacrylamide,N-acetylmethacrylamide, N-propionylmethacrylamide,N-(p-chlorobenzoyl)methacrylamide and the like.

(12) Unsaturated carboxylic acids such as acrylic acid, methacrylicacid, maleic anhydride, itaconic acid and the like.

As the aqueous alkali solution-soluble polymer compound in thisembodiment, compounds having a weight average molecular weight of 2000or more and a number average molecular weight of 500 or more arepreferable from the standpoint of film strength, irrespective of ahomopolymer or copolymer. Further preferable compounds have a weightaverage molecular weight of 5000 to 300000 and a number averagemolecular weight of 800 to 250000, and a degree of dispersion (weightaverage molecular weight/number average molecular weight) of 1.1 to 10.

In the above-mentioned copolymer, the compounding ratio by weight of amonomer having an acidic group (b-1) to (b-3) to other monomer ispreferably in the range from 50:50 to 5:95, more preferably in the rangefrom 40:60 to 10:90 from the standpoint of development latitude.

As the polymer compound having a phenolic hydroxyl group preferable inthe present embodiment, there are listed novolak resins such as apolycondensate of m-/p-mixed cresol with formaldehyde, a polycondensateof phenol and cresol and formaldehyde, and the like, a copolymer ofN-(4-hydroxyphenyl) methacrylamide/methyl methacrylate/acrylonitrile, acopolymer of 2-(N′-4-hydroxyphenyl)ureido)ethyl methacrylate/methylmethacrylate/acrylonitrile, and the like.

As the polymer compound having a sulfoneamide group preferable in thepresent embodiment, there are listed a copolymer ofN-(p-aminosulfonylphenyl)methacrylamide/methylmethacrylate/acrylonitrile, and the like, and as the polymer compoundhaving an active imide group, there are listed a copolymer ofN-(p-toluenesulfonyl)methacrylamide/methylmethacrylate/acrylonitrile/2-hydroxyethyl methacrylate, and the like.

These aqueous alkali solution-soluble polymer compounds may be usedalone or in combination of two or more, and used in a addition amount of30 to 99% by weight, preferably of 40 to 95% by weight, particularlypreferably of 50 to 90% by weight based on the total solid content of aphotosensitive composition. When the addition amount of the aqueousalkali solution-soluble polymer compound is less than 30% by weight,durability of a recording layer deteriorates, while when over 99% byweight, both of sensitivity and durability are not preferable.

[Other components]

In a photosensitive composition of the present embodiment, variousadditive can further be added, if necessary. For example, when otheronium salt, aromatic sulfone compound, aromatic sulfonate compound,polyfunctional amine compound and the like are added, an ability tosuppress dissolution of an aqueous-alkali-solution-soluble polymer to adeveloper can be improved, meaning preferable phenomenon.

As the above-mentioned onium salt a diazonium salt, ammonium salt,phosphonium salt, iodonium salt, sulfonium salt, selenonium salt,arsonium salt and the like are listed. Preferably examples of the oniumsalt used in the present embodiment include diaoznium salts described inS. I. Schlesinger, Photogr. Sci. Eng., 18, 387 (1974), T. S. Bal et al,Polymer 21. 423 (1980), or JP-A No. 5-158230, ammonium salts describedin U.S. Pat. Nos. 4,069,055 and 4,069,056 or JP-A No. 3-140140,phosphonium salts described in D. C. Necker et al, Macromolecules, 17,2468 (1984), C. S. Wen et al, The, Proc. Conf. Rad. Curing ASIA, p478Tokyo, October (1988), U.S. Pat. Nos. 4,069,055 or 4,069,056, iodoniumsalts described in J. V. Crivello et al, Macromolecules, 10(6), 1307(1977), Chem. & Eng. News, Nov. 28, p31 (1988), EU Patent No. 104,143,U.S. Pat. Nos. 339,049, 410,201, JP-A No. 2-150848 or 2-296514,sulfonium salts described in J. V. Crivello et al., Polymer J. 17, 73(1985), J. V. Crivello et al., J. Org. Chem., 43, 3055 (1978), W. R.Watt et al, J. Polymer Sci., Polymer Chem. Ed., 22, 1789 (1984), J. V.Crivello et al., Polymer Bull., 14, 279 (1985), J. V. Crivello et al.,Macromolecules, 14(5), 1141 (1981), J. V. Crivello et al., J. PolymerSci., Polymer Chem. Ed., 17, 1877 (1979), EU Patent Nos. 370,693,233,567, 297,443, 297,442, U.S. Pat. Nos. 4,933,377, 3,902,114, 410,201, 339,049, 4,760,013, 4,734,444, 2,833,827, German Patent Nos.2,904,626, 3,604,580, 3,604,581, selenonium salts described in J. V.Crivello et al., Macromolecules, 10(6), 1307 (1977), or J. V. Crivelloet al., J. Polymer Sci., Polymer Chem. Ed., 17, 1047 (1979), arsoniumsalts described in C. S. Wen et al., The, Proc. Conf. Rad. Curing ASIA,p478 Tokyo, October (1988), and the like.

As the counter ion of the above-mentioned onium salt, there are listedtetrafluoroboric acid, hexafluorophophosric acid,triisopropylnaphthalenesulfonic acid, 5-nitro-o-toluenesulfonic acid,5-sulfosalicyclic acid, 2,5-dimethylbenzenesulfonic acid, 2,4,6-trimethylbenzenesulfonic acid, 2-nitrobenzenesulfonic acid,3-chlorobenzenesulfonic acid, 3-bromobenzenesulfonic acid,2-fluorocaprylnaphthalenesulfonic acid, dodecylbenzenesulfonic acid,1-naphthol-5-sulfonic acid,2-methoxy-4-hydroxy-5-benzoyl-benzenesulfonic acid, p-toluenesulfonicacid and the like.

Among them, particularly, hexafluoride phosphoric acid andtriisopropylnaphthalenesulfonic acid, and alkyl aromatic sulfonic acidssuch as 2,5-dimethylbenzenesulfonic acid and the like, are suitable.

The above-mentioned onium salt is added in an amount preferably of 1 to50% by weight, more preferably of 5 to 30% by weight, particularlypreferably of 10 to 30% by weight, based on the total solid content ofmaterials constituting the first layer.

For further improving sensitivity, cyclic acid anhydrides, phenols,organic acids can be used simultaneously. As the cyclic acid anhydride,there are listed phthalic anhydride, tetrahydrophthalic anhydride,hexahydrophthalic anhydride, 3.6-endooxy-Δ4-tetrahydrophthalicanhydride, tetrachlorophthalic anhydride, maleic anhydride, chloromaleicanhydride, α-phenylmaleic anhydride, succinic anhydride, pyromelliticanhydride and the like as described in U.S. Pat. No. 4,115,128. As thephenols, there are listed bisphenol A, p-nitrophenol, p-ethoxyphenol,2,4,4′-trihydroxybenzophenone, 2,3,4-trihydroxybenzophenone,4-hydroxybenzophenone, 4,4′,4″-trihydroxytriphenylmethane,4,4′,3″,4″-tetrahydroxy-3,5,3′,5′-tetramethyltriphenylmethane and thelike. Further, as the organic acids, there are listed sulfonic acids,sulfinic acid, alkylsulfuric acids, phosphonic acids, phosphates andcarboxylic acids described in JP-A Nos. 60-88942 and 2-96755 and thelike, and specific examples thereof include p-toluenesulfonic acid,dodecylbenzensulfonic acid, p-toluenesulfinic acid, ethylsulfuric acid,phenylphosphonic acid phenylphosphinic acid, phenyl phosphate, diphenylphosphate, benzoic acid, isophthalic acid, adipic acid, p-toluic acid,3,4-dimethoxybenzoic acid, phthalic acid, terephthalic acid,4-cyclohexene-1,2-dicarboxylic acid, erucic acid, lauric acid,n-undecanoic acid, ascorbic acid and the like.

The proportion of the above-mentioned cyclic acid anhydrides, phenolsand organic acids occupying a printing material is preferably from 0.05to 20% by weight, more preferably from 0.1 to 15% by weight,particularly preferably from 0.1 to 10% by weight.

In a printing plate material of the present embodiment, nonionicsurfactants described in JP-A Nos. 62-251740 and 3-208514, andampholytic surfactants described in JP-A Nos. 59-121044 and 4-13149 canbe added, for increasing stability of treatment against developingconditions.

Specific examples of the nonionic surfactant include sorbitantristearate, sorbitan monopalmitate, sorbitan trioleate, stearic acidmonoglyceride, polyoxyethylene nonylphenyl ether and the like.

Specific examples of the ampholytic surfactant includealkyldi(aminoethyl)glycine, alkylpolyaminoethylglycine hydrochloride,2-alkyl-N-carboxyethyl-N-hydroxyethylimidazolinium betaine andN-tetradecyl-N,N-betaine type compounds (for example, trade name:“Amogen K”, manufactured by Daiichi Kogyo K.K.), and the like.

The proportion of the above-mentioned nonionic surfactants andampholytic surfactants occupying a printing plate material is preferablyfrom 0.05 to 15% by weight, more preferably from 0.1 to 5% by weight.

To a printing plate material of the first embodiment, a printing-outagent for providing a visible image immediately after heating byexposing; and a pigment or a dye as an image coloring agent can beadded.

As the printing-out agent, a combination of a compound (a photo-acidemitting agent) capable of emitting an acid by heating by exposure andan organic dye capable of forming a salt can be typically enumerated.Specifically, a combination of o-naphthoquinoneazido-4-sulfonic acidhalogenide and a salt-forming organic dye, as disclosed in each of JP-ANos. 50-36209 and 53-8128; and a combination of trihalomethyl compoundand a salt-forming organic dye, as disclosed in each of JP-A Nos.53-36223, 54-74728, 60-3626, 61-143748, 61-151644 and 63-58440 can beenumerated. As the trihalomethyl compound, there exist an oxazolecompound and a triazine compound, each of which is excellent intime-stability and provides a distinct printing-out image.

As the image coloring agent, other dyes can be used in addition to theabovementioned salt-forming organic dye. As suitable dyes, an oilsoluble dye and a basic dye can be enumerated as well as thesalt-forming organic dye. Specifically, Oil Yellow #101, Oil Yellow#103, Oil Pink #312, Oil Green BG, Oil Blue BOS, Oil Blue #603, OilBlack BY, Oil Black BS and Oil Black T-505 (which manufactured by ORIENTCHEMICALS Ltd.), Victoria Pure Blue, Crystal Violet (CI42555), MethylViolet (CI42535), Ethyl Violet, Rhodamine B(CI145170B), Malachite Green(CI42000), Methylene Blue (CI52015) and the like can be enumerated.Indeed, dyes disclosed in JP-A No. 62-293247 are in particularpreferred. These dyes can be added to a printing plate material in aratio of 0.01 to 10% by weight, preferably 0.1 to 3% by weight of thewhole solids of the printing plate material.

Additionally, to the printing plate material of the first embodiment, ifnecessary, a plasticizer may be added in order to provide theflexibility for a coating. As the plasticizer, for example,poly(ethylene glycol), tributyl citrate, diethyl phthalate, dibutylphthalate, dihexyl phthalate, dioctyl phthalate, tricresyl phosphate,tributyl phosphate, trioctyl phosphate, tetrahydrofurfuryl oleate, anoligomer and a polymer of acrylic acid or methacrylic acid, and the likecan be used.

Furthermore, in addition thereto, an epoxy compound; vinyl ethers; and aphenol compound having an alkoxymethyl group and a phenol compoundhaving a hydroxymethyl group as disclosed in JP-A No. 8-276558; and acrosslinking compound having an action of inhibiting alkali dissolutionas disclosed in Japanese Patent Application No. 9-328937; or the likecan be suitably added thereto according to an object.

A planographic printing plate of the present embodiment can be producedby dissolving in a solvent the components of the photosensitive layercoating solution containing the photosensitive component of the presentembodiment and the components of a coating solution for a desired layersuch as a protecting layer, and applying the coating solution(s) on anappropriate support. Hereupon, as the solvent used, ethylene dichloride,cyclohexanone, methyl ethyl ketone, methanol, ethanol, propanol,ethylene glycol monomethyl ether, 1-methoxy-2-propanol,2-methoxyethylacetate, 1-methoxy-2-propylacetate, dimethoxyethane,methyl lactate, ethyl lactate, N, N-dimethylacetoamide,N,N-dimethylformamide, tetramethylurea, N-methylpyrrolidone, dimethylsulfoxide, sulfolane, γ-butyrolactone, toluene, water and the like canbe enumerated, to which the solvent is not limited. Each of the solventsis used by alone or in the form of a mixture. The concentration of theabove component (as the whole solids including an additive agent) in asolvent is preferably 1 to 50% by weight. Furthermore, an applied amount(as solids) to a substrate as obtained after applying and drying, whichis varied according to a use, is commonly and preferably 0.5 to 5.0 g/m²as for a photosensitive printing plate.

As a method of coating, various methods can be used, for example,Bar-coater coating, Rotation coating, Spray coating, Curtain coating,Dip coating, Air knife coating, Blade coating, Roll coating and the likecan be enumerated. The smaller an applied amount becomes, the greater anapparent photographic sensitivity becomes, but the film properties of aphotosensitive layer are decreased.

To a coating liquid applied to a photosensitive layer in which aphotosensitive composition of the first embodiment is used, a surfactantto improve applicability, for example, a fluorine-containing surfactantas disclosed in JP-A No. 62-170950 can be added. An amount to be addedis preferably 0.01 to 1% by weight, more preferably 0.05 to 0.5% byweight of the whole printing plate material.

As a substrate which is used for a planographic printing plate in thefirst embodiment, a flat material which is stable in dimension, forexample, paper; paper to which a plastic such as polyethylene,polypropylene or polystyrene is laminated; a plate of a metal such asaluminum, zinc or copper; a film of a plastic such as cellulosediacetate, cellulose triacetate, cellulose propionate, cellulosebutyrate, cellulose acetate butyrate, cellulose nitrate, poly(ethyleneterephthalate), polyethylene, polystyrene, polypropylene, polycarbonate,poly(vinyl acetal); paper or a plastic film to which a metal asmentioned above is laminated or deposited; and the like are included.

As a substrate which is used for a planographic printing plate of thefirst embodiment, a polyester film and an aluminum plate are preferred,and an aluminum plate, which is stable in dimension and relativelycheap, is in particular preferred among others. A suitable aluminumplate is a pure aluminum plate or an alloyed plate including aluminum asa main component and including a different element(s) in a very smallamount, and furthermore a plastic film to which aluminum is laminated ordeposited is also suitable. The different element(s) which may beincluded in the aluminum alloy includes silicon, iron, manganese,copper, magnesium, chromium, zinc, bismuth, nickel, titanium or thelike. The content of the different element(s) in the alloy is 10% byweight or less. A particularly suitable aluminum in the presentinvention is a pure aluminum. However, as it is difficult to manufacturea perfectly pure aluminum in terms of current refining technologies,aluminum including a different element(s) in a very small amount may beused. Thus, an aluminum plate as applied to the present invention is notspecified in composition, and a suitable aluminum plate which isconventionally and publicly known or used as a raw material can beutilized. The thickness of an aluminum plate used in the presentinvention is approximately 0.1 mm to 0.6 mm, preferably 0.15 mm to 0.4mm, more preferably 0.2 mm to 0.3 mm.

Before surface-roughening an aluminum plate, if desired, a degreasingtreatment with a surfactant, an organic solvent, an alkaline aqueoussolution or the like is carried out so as to remove a rolling oil on thesurface thereof.

A surface-roughening treatment for the surface of an aluminum plate iscarried out according to various methods: for example, a method ofmechanically surface-roughening, a method of surface-roughening byelectrochemically dissolving the surface, and a method ofsurface-roughening by chemically and selectively dissolving the surface.As the mechanical surface-roughening method, a publicly known methodsuch as Ball Polishing method, Brush Polishing method, Blast Polishingmethod, or Buff Polishing method can be used. As the electrochemicalsurface-roughening method, a method of using alternating current ordirect current in an electrolyte of hydrochloric acid or nitric acid isenumerated. Furthermore, amethod in which both are combined with eachother, as disclosed in JP-A No. 54-63902, can be also utilized.

A surface-roughened aluminum plate as mentioned above is, if necessary,subjected to an alkaline etching and neutralizing processes, andthereafter, if desired, anodized so as to enhance water-holdingproperties and wear and abrasion resistance. As an electrolyte as usedfor anodizing the aluminum plate, various electrolytes capable offorming a porous oxide film can be used. Commonly, sulfuric acid,phosphoric acid, oxalic acid, chromic acid, or a mixed acid thereof canbe used. The concentration of such an electrolyte is properly determineddepending upon a type of the electrolyte.

Conditions for anodizing treatment may change depending upon anelectrolyte used, and thus can not be wholly specified. However, asolution having an electrolyte concentration of 1 to 80% by weight; aliquid temperature of 5° to 70° C.; a current density of 5 to 60 A/dm²;a voltage of 1 to 100 V; and an electrolysis time of 10 seconds to 5minutes are generally suitable.

When an amount of an anodic oxide film is less than 1.0 g/m², durabilityis not sufficient, scratches are easily made on the non-image area ofplanographic printing plate, and thus ink tends to attach to thescratched area on printing; namely, “scratch-stains” are easily caused.

After anodizing treatment, the surface of aluminum is, if necessary,subjected to a treatment for increasing hydrophilicity. As ahydrophilicity treatment as used in the first embodiment, there existsAlkaline Metal Silicate method (in which for example, an aqueoussolution of sodium silicate is used), which is disclosed in U.S. Pat.Nos. 2,714,066; 3,181,461; 3,280,734; and 3,902,734. In this method, asubstrate is immersed into an aqueous solution of sodium silicate, orelectrolyzed therein. In addition, a method of treating with potassiumzirconate fluoride as disclosed in JP-B No. 36-22063; and a method oftreating with poly(vinyl phosphonic acid) as disclosed in U.S. Pat. Nos.3,276,868, 4,153,461, and 4,689,272; or the like may be used.

A planographic printing plate of the present invention is the one inwhich a positive type photosensitive layer including a photosensitivecomposition of the present invention is provided on its substrate.However, if necessary, an under coat can be provided between thesubstrate and the photosensitive layer.

As a component of the under coat, various organic compounds are used.The component is selected from the group consisting of carboxymethylcellulose; dextrin; gum arabic; a phosphonic acid having amino group,such as 2-aminoethylphosphonic acid; an organic phosphonic acid whichmay have a substituent(s), such as phenylphosphonic acid,naphthylphosphonic acid, alkylphosphonic acid, glycerophosphonic acid,methylenediphosphonic acid, or ethylenediphosphonic acid; an organicphosphoric acid which may have a substituent(s), such asphenylphosphoric acid, naphthylphosphoric acid, alkylphosphoric acid, orglycerophosphoric acid; an organic phosphinic acid which may have asubstituent(s), such as phenylphosphinic acid, naphthylphosphinic acid,alkylphosphinic acid, or glycerophosphinic acid; an amino acid such asglycine, β-alanine; an amine hydrochloride having hydroxy group, such astriethanolamine hydrochloride; and the like, and may be used as amixture of two or more thereof.

The organic under coat can be provided according to the followingmethods: amethodof providing the organic under coat, comprising thesteps of: dissolving the organic compound mentioned above in an organicsolvent such as methanol, ethanol or methyl ethyl ketone, or water, or amixed solvent thereof, applying the solution onto an aluminum plate, anddrying the same; and a method of providing the organic under coat,comprising the steps of: dissolving the organic compound mentioned abovein an organic solvent such as methanol, ethanol or methyl ethyl ketone,or water, or a mixed solvent thereof, immersing an aluminum plate intothe solution such that the aluminum plate adsorbs the compound abovethereon, and thereafter washing the same with water or the like, anddrying the same. In the former method, a solution including the organiccompound described above in a concentration of 0.005 to 10% by weightcan be applied according to various manners, while in the latter method,a solution having a concentration of 0.01 to 20% by weight, preferably0.05 to 5% by weight; an immersion temperature of 20 to 90° C.,preferably 25 to 50° C.; an immersion time of 0.1 second to 20 minutes,preferably 2 seconds to 1 minute can be employed. A solution used inthese methods can be adjusted to a pH of 1 to 12 with a basic materialsuch as ammonia, triethylamine, potassium hydroxide, and/or an acidicmaterial such as hydrochloric acid or phosphoric acid. Furthermore, ayellow dye can be added thereto so as to improve the tonereproducibility of an image recording material.

The amount to be applied of the organic under coat is suitably 2 to 200mg/m², preferably 5 to 100 mg/m². When the applied amount is less than 2mg/m², plate wear performance can not be sufficiently provided. When theapplied amount is more than 200 mg/m², the results are not satisfactory,either.

A positive type planographic printing plate as produced as mentionedabove is usually subjected to an image exposure and developingtreatment.

As a source for active light used for the image exposure, a solid-statelaser and a semiconductor laser which can radiate infrared rays havingwave length of 760 to 1200 nm can be enumerated.

In this embodiment, a light source having an emission wave lengthbetween a near-infrared area to an infrared area is preferred, andaccordingly, a solid-state laser and a semiconductor laser is inparticular preferred.

As a developing solution and a replenisher for a planographic printingplate of the first embodiment, an alkaline aqueous solution asconventionally known can be used, and inorganic alkaline salts such assodium silicate, potassium silicate, sodium tertiary phosphate,potassium tertiary phosphate, ammonium tertiary phosphate, sodiumsecondary phosphate, potassium secondary phosphate, ammonium secondaryphosphate, sodium carbonate, potassium carbonate, ammonium carbonate,sodium hydrogencarbonate, potassium hydrogencarbonate, ammoniumhydrogencarbonate, sodium borate, potassium borate, ammonium borate,sodium hydroxide, ammonium hydroxide, potassium hydroxide and lithiumhydroxide can be enumerated. Besides, organic alkaline agents such asmonomethylamine, dimethylamine, trimethylamine, monoethylamine,diethylamine, triethylamine, monoisopropylamine, diisopropylamine,triisopropylamine, n-butylamine, monoethanolamine, diethanolamine,triethanolamine, monoisopropanolamine, diisopropanolamine,ethyleneimine, ethylenediamine, pyridine can be also used.

Each of these alkaline agents is used by alone, or as a mixture of twoor more thereof.

Particularly preferred developing solutions among these alkaline agentsare an aqueous solution of a silicate such as sodium silicate orpotassium silicate, because developing properties can be adjusted by aratio of silicon oxide SiO₂ which is one of components of the silicatesto an alkaline metal oxide M₂0 and each concentration thereof. Forexample, an alkaline metal silicate as disclosed in JP-A No. 54-62004 orJP-B No. 57-7427 is effectively used.

Additionally, when development is carried out by using an automaticprocessor, it is known that an aqueous solution (namely, a replenisher)having an alkaline strength higher than that of a developing solution isadded thereto, and thereby a lot of PS plates can be treated withoutchanging the developing solution in a developing tank for a long periodof time. In an embodiment of the present invention also, thisreplenisher system is preferably applied. In order to conduct theacceleration and control of developing properties, and enhance thediffusion of residuals generated during development and the affinity ofthe PS plates with ink at a printing image area, various surfactantsand/or organic solvents can be added to the developing solution and thereplenisher if necessary. As preferable surfactants, anionic, cationic,nonionic and amphoteric surfactants can be enumerated.

Furthermore, if necessary, a reducing agent such as hydroquinone;resorcin; a sodium salt or potassium salt of an inorganic acid such assulfurous acid or hydrogensulfurous acid; an organic carboxylic acid; adefoaming agent; a water softener can be added to the developingsolution and the replenisher.

A printing plate which was developed by using the developing solutionand the replenisher above is post-treated with washing water; a risingsolvent including a surfactant or the like; and a desensitizing liquidincluding gum arabic and/or a starch derivative. As post-treatment whenan image recording material in an embodiment of the present invention isused as a printing plate, various combinations of the treatments abovecan be employed.

Recently, in the industry of plate making or printing, for the purposeof rationalization and standardization of printing work, an automatic(developing) processor is broadly used for printing plates. Such anautomatic processor commonly comprises a processing portion and apost-treating portion. More specifically, an automatic processorcomprises an apparatus for conveying a printing plate, processing liquidtanks and a spraying apparatus, in which processor an exposed printingplate is horizontally conveyed, and each treating liquid, as it ispumped up, is sprayed from a spray nozzle so as to effect the developingprocess. In addition, in recent years, a method in which a printingplate is immersed in the processing liquids charged in the processingliquids tanks and transferred in the processing liquids by guide rollsis also known. According to such an automatic processing, it is possibleto add a replenisher to each processing liquid, depending upon aprocessing amount, operating hours and the like.

Additionally, a method of processing with a substantially freshprocessing liquid, that is, an expendable system can be also applied.

A photosensitive planographic printing plate in which a photosensitivecomposition of the first embodiment is used will be explained. Whenthere exists an unnecessary image area (for example, the print of a filmedge of original image film, and the like) on the planographic printingplate which has been subjected to image exposure, development, waterwashing and/or rinsing and/or gumming, the unnecessary image area is tobe erased. In order to erase the unnecessary image, for example, amethod comprising the steps of applying an erasing liquid to theunnecessary image area, leaving the same as it is for a predeterminedperiod of time, and thereafter water washing the same is preferablyused, as disclosed in JP-B No. 2-13293. Besides, a method comprising thesteps of: illuminating an active light introduced through an opticalfiber onto the unnecessary image area; and thereafter developing can bealso utilized, as disclosed in JP-A No. 59-174842.

To the planographic printing plate as obtained as mentioned above, adesensitizing gum can be coated if desired, and thereafter theplanographic printing plate is subjected to printing step. However, whena planographic printing plate having a higher plate wear is desired, aburning treatment is applied thereto.

When a planographic printing plate is subjected to a burning treatment,it is preferred to treat it with a counter-etching liquid as disclosedin each of JP-B Nos. 61-2518 and 55-28062, and JP-A Nos. 62-31859 and61-159655, prior to the burning treatment.

As a method therefor, a method of applying the counter-etching liquidonto the planographic printing plate by using a sponge or an absorbentcotton into which the counter-etching liquid is impregnated, orimmersing the planographic printing plate into a butt which is filledwith the counter-etching liquid; or a method of coating by using anautomatic coater is applied. Additionally, by homogenizing the appliedamount by using a squeegee or a squeegee roller after applying orcoating, more preferable results are provided.

The applied amount of the counter-etching liquid is commonly andsuitably 0.03 to 0.8 g/m² (as dry weight).

The planographic printing plate to which the counter-etching liquid isapplied is dried if necessary, and thereafter heated at an elevatedtemperature by using a burning processor (for example, a burningprocessor “BP-1300” as sold by Fuji Photo Film Co., Ltd.), wherein theheat temperature is preferably in the range of 180° to 300° C., and theheat time is in the range of 1 to 20 minutes, depending upon the type ofcomponents forming an image.

The planographic printing plate as burning-treated can be, if necessary,subjected to treatments such as water-washing and gumming, which areconventionally carried out. However, when a counter-etching liquidincluding awater-soluble polymer compound is used, gumming and the like,that is, a desensitizing treatment can be omitted.

The planographic printing plate as provided by treatments mentionedabove is subjected to an offset press or the like so as to use for a lotof printing.

EXAMPLES

Hereinafter, the first embodiment will be exemplified according toExamples. However, the scope of the first embodiment is not intended tobe limited by the Examples.

Examples 1 to 4

[Preparation of Substrates]

An aluminum plate (Material: 1050) having a thickness of 0.3 mm waswashed and degreased with trichloroethylene, and thereafter this surfacewas subjected to graining by using a nylon brush and a 400 meshpumice/water suspension, and then cleanly washed with water. This platewas immersed into an aqueous solution of 25% of sodium hydroxide at atemperature of 45° C. for a period of 9 seconds so as to etch the plate.After washing with water, the plate was furthermore immersed into a 20%nitrous acid for a period of 20 seconds, and water-washed, so that theetched amount on the surface by graining was about 3 g/m². Next, thisplate was anodized by a direct current at a current density of 15 A/dm²using a 7% sulfuric acid as an electrolyte so as to form an anodizedfilm thereupon in an amount of 3 g/m², and thereafter water-washed, anddried so as to obtain substrates A. The following primer coating liquidwas applied to the substrates A, and the consequent films were dried ata temperature of 90° C. for a period of one minute so as to obtainsubstrates B. The applied amount of the films after drying was 10 mg/m².

<Composition of Primer Coating Liquid> β-alanine 0.5 g Methanol 95 gWater 5 g

The following photosensitive liquids 1 in which infrared absorbingagents are varied as shown in the following Table 1 were prepared, andeach of the photosensitive liquids 1 was applied to the resultantsubstrate above so as to obtain an applied amount of 1.8 g/m², and thusplanographic printing plates for Examples 1 to 4 were provided.

<Composition of Photosensitive Liquids 1> m, p-cresolnovolak 1.0 g (m/pratio = 6/4; weight average molecular weight = 3500; with 0.5% by weightof non-reacted cresol) (alkaline water soluble polymer compound)Infrared absorbing agents as described 0.2 g in Table 1 (compoundsrepresented by the general formula (I)) Dye in which a counter anion of0.02 g victoria-pure-blue BOH is replaced with 1-naphthalenesulfonicacid anion Fluorine-contained surfactant 0.05 g (MEGAFAC F-177;manufactured by DAINIPPON INK AND CHEMICALS, INC.) γ-Butyrolactone 3 gMethylethyl ketone 8 g 1-Methoxy-2-propanol 7 g

Comparative Example 1

A planographic printing plate in Comparative Example 1 was prepared inthe substantially same manner as the one in Example 1, except thatinfrared absorbing agents as represented by the general formula (I) asincorporated into photosensitive liquids 1 were replaced with aninfrared absorbing agent B-1 as represented by the following structure.

Examples 5 to 8

<Example of Synthesis (Copolymer 1)>

31.0 g (0.36 moles) of methacrylic acid, 39.1 g (0.36 moles) of ethylchloroformate and 200 ml of acetonitrile were introduced into a threeneck flask of 500 ml as provided with a stirrer, a condenser tube and adropping funnel, and the mixture was stirred, while the mixture wascooled on an ice bath. Into the mixture, 36.4 g (0.36 moles) oftriethylamine was dropped through the dropping funnel over about onehour. After the dropping was finished, the ice bath was removed, and themixture was stirred at a room temperature for a period of 30 minutes.

To this reactant mixture, 51.7 g (0.30 moles) ofp-aminobenzensulfonamide was added, and the mixture was stirred for aperiod of one hour, while heating at a temperature of 70° C. with an oilbath. After the reaction was finished, this mixture was added to oneliter of water, while the water was stirred, and the consequent mixturewas stirred for a period of 30 minutes. The mixture was filtrated toseparate a deposit, this deposit was slurried with 500 ml of water, andthereafter this slurry was filtrated, and the consequent solids weredried so as to obtain a white solid of N-(p-aminosulfonylphenyl)methacrylamide (with a yield of 46.9 g).

Next, 4.61 g (0.0192 moles) of N-(p-aminosulfonylphenyl)methacrylamide,2.94 g (0.0258 moles) of ethyl methacrylate, 0.80 g (0.015 moles) ofacrylonitrile and 20 g of N,N-dimethylacetamide were introduced into athree neck flask of 20 ml as provided with a stirrer, a condenser tubeand a dropping funnel, and the mixture was stirred, while the mixturewas heated at a temperature of 65° C. on a hot water bath. Into themixture, 0.15 g of “V-65” (manufactured by Wako Pure ChemicalIndustries, Ltd.) was added, and the mixture was stirred for 2 hoursunder a nitrogen flow, while a temperature of 65° C. was maintained. Tothis reactant mixture, a blend of 4.61 g ofN-(p-aminosulfonylphenyl)methacrylamide, 2.94 g of ethyl methacrylate,0.80 g of acrylonitrile, N,N-dimethylacetamide and 0.15 g of “V-65” wasdropped through the dropping funnel over two hours. After the droppingwas finished, the consequent mixture was furthermore stirred at atemperature of 65° C. for a period of two hours. After the reaction wasfinished, 40 g of methanol was added to the mixture, cooled, and theconsequent mixture was added to 2 liters of water, while the water wasstirred. After the mixture was stirred for a period of 30 minutes, adeposit was filtered out, separated and dried so as to obtain 15 g of awhite solid. A gel permeation chromatography was used to determine ofthe weight average molecular weight (on the basis of polystyrene) ofthis copolymer 1. As a result, the weight average molecular weight was53,000.

The following photosensitive liquids 2 in which infrared absorbingagents are varied as shown in the following Table 1 were prepared, andeach of the photosensitive liquids 2 was applied to the same substrateas the one used in Examples 1 to 4, so that an applied amount was 1.8g/m². Accordingly, planographic printing plates for Examples 5 to 8 wereprovided.

<Composition of Photosensitive Liquids 2> The above-mentioned copolymer1 0.75 g (alkaline water soluble polymer compound) m, p-cresolnovolak0.25 g (m/p ratio = 6/4; weight average molecular weight = 3500; with0.5% by weight of non-reacted cresol) (alkaline water soluble polymercompound) Tetrahydrophthalic anhydride 0.03 g Infrared absorbing agentsas described 0.017 g in Table 1 (compounds represented by the generalformula (I)) Dye in which a counter anion of 0.015 g victoria-pure-blueBOH is replaced with 1-naphthalenesulfonic acid anion Fluorine-containedsurfactant 0.05 g (MEGAFAC F-177; manufactured by DAINIPPON INK ANDCHEMICALS, INC.) γ-Butyrolactone 10 g Methylethyl ketone 10 g1-Methoxy-2-propanol 1 g

Comparative Example 2

A planographic printing plate in Comparative Example 2 was prepared inthe substantially same manner as the one in Example 5, except thatinfrared absorbing agents as represented by the general formula (I) asincorporated into photosensitive liquids 2 were replaced with aninfrared absorbing agent B-1 represented by the above-mentionedstructure.

[Performance Evaluation of Planographic Printing Plate]

On each of the planographic printing plates in Examples 1 to 8 andComparative Examples 1 and 2, which were produced as mentioned above,performance evaluation was made according to the following criteria. Theresults of evaluation are shown in Table 1.

Image Forming Properties: Evaluation of Sensitivity and DevelopmentLatitude

The obtained planographic printing plates were exposed by using asemiconductor laser having a wave length of 840 nm, and developed byusing an automatic processor (manufactured by Fuji Photo Film Co., Ltd.“PS processor 900VR”) in which developing solution DP-4 and rinse liquidFR-3 (1:7) manufactured by Fuji Photo Film Co., Ltd. were charged,wherein DP-4 was used at dilution ratios of two levels of 1:6 and 1:12.The width of line at a non-image area as obtained with each developingsolution was determined, and a radiation energy of a laser correspondingto the line width was determined, which was used as sensitivity. Then,differences between what was diluted at a ratio of 1:6 which is thestandard and what was diluted at a ratio of 1:12 were recorded. Thesmaller the differences are, the better the development latitude is, andthe value of 20 mJ/cm² or less represents a practicable level.

Evaluation of Preservation Stability

The consequent planographic printing plates were preserved at atemperature of 60° C. for a period of 3 days prior to the exposure to alaser, and thereafter a laser exposure and a development were carriedout in the same manner as the one mentioned above, and a sensitivity wasdetermined in the same manner so as to compare with the results asmentioned above. When the fluctuation of sensitivity is 20 mJ/cm² orless, preservation stability was evaluated to be excellent and to be ona practically acceptable level (which is a level which does not presentany problems in actual practice).

TABLE 1 Development Infrared Sensitivity Latitude Preservation AbsorbingAgent (mJ · cm²) (mJ · cm²) Stability Example 1 IR-2 125 10 Good Example2 IR-7 120 15 Good Example 3 IR-12 120 15 Good Example 4 IR-22 125 10Good Comparative B-1 145 25 Bad example 1 Example 5 IR-2 115 5 GoodExample 6 IR-7 115 10 Good Example 7 IR-12 110 10 Good Example 8 IR-22115 5 Good Comparative B-1 135 25 Bad example 2

From the results shown in Table 1, it is found that, as compared withplanographic printing plates in Comparative Examples 1 and 2 in which aninfrared absorbing agent B-1 not having at the N-position a long-chainalkyl group is used, each of planographic printing plates in Examples 1to 10 is high in sensitivity to an infrared laser. Furthermore, in eachof planographic printing plates of Examples 1 to 10, a difference insensitivity between two developing solutions having a different dilutedconcentration is 20 mJ/cm² or less which is practically acceptablelevel, and thus it has been confirmed that these planographic printingplates are excellent in developing latitude.

Besides, from the results of evaluation of preservation stability, ithas been confirmed that, in all of the planographic printing plates ofthe first embodiment, a fluctuation in the sensitivity between beforeand after preservation is 20 mJ/cm² or less which is practicallyacceptable level. Therefore, the planographic printing plates ofembodiments of the present invention are evaluated to be also excellentin preservation stability.

Examples 9 to 12

The substrate A used in Example 5 was treated with an aqueous solutionof 2.5% by weight of sodium silicate at a temperature of 30° C. for aperiod of 10 seconds, and coated with the following primer coatingliquid, and the film was dried at a temperature of 90° C. for a periodof one minute so as to obtain a substrate C. The applied amount of thefilm after drying was 15 mg/M².

<Composition of Primer Coating Liquid> Following copolymer having  0.3 ga molecular weight of 28000 Methanol 100 g Water  1 g

Molecular Weight 28,000

The same photosensitive liquids 2 as the ones used in Examples 5 to 8were applied to the obtained substrates C so that an applied amount was1.8 g/m², to obtain planographic printing plates for Examples 9 to 12.

Comparative Example 3

A planographic printing plate in Comparative Example 3 was prepared inthe substantially same manner as the one in Example 9, except thatinfrared absorbing agents as represented by the general formula (I) asincorporated into photosensitive liquids 1 were replaced with aninfrared absorbing agent B-1 as represented by the above-mentionedstructure.

Each of the obtained planographic printing plates in Examples 9 to 12and Comparative Example 3 was exposed at a main scanning speed of 5m/second by using a semiconductor laser having an output of 500 mW, awave length of 830 nm and a beam diameter of 17 μm (1/e²), andthereafter developed by using an automatic processor “PS processor900VR” (manufactured by Fuji Photo Film Co., Ltd.) into which twodeveloping solutions (namely, a developing solution 1 and a developingsolution 2) each having a different dilution ratio and the compositionas shown below; and a rinsing liquid FR-3 (which is diluted at a ratioof 1:7) were charged. Then sensitivities and development latitudesthereof were recorded. Furthermore, the evaluation of preservationstability was made in the same manner as the one in Examples 1 to 8.

The results are shown in Table 2.

TABLE 2 <Developing Solution 1> D-sorbitol 5.1 parts by weight Sodiumhydroxide 1.1 parts by weight Triethanolamine, 0.03 parts by weightethylene oxide additives (30 moles) Water 93.9 parts by weight<Developing Solution 2> D-sorbitol 5.1 parts by weight Sodium hydroxide1.1 parts by weight Triethanolamine, 0.03 parts by weight ethylene oxideadditives (30 moles) Water 140.7 parts by weight Development InfraredSensitivity Latitude Preservation Absorbing Agent (mJ · cm²) (mJ · cm²)Stability Example 9 IR-2 120 10 Good Example 10 IR-7 115 10 Good Example11 IR-12 115 10 Good Example 12 IR-22 110  5 Good Comparative B-1 140 20Slightly Bad example 3

From the results shown in Table 2, it is found that, as compared with aplanographic printing plate in Comparative Example 3 in which aninfrared absorbing agent B-1 not having at the N-position a long-chainalkyl group is used, each of planographic printing plates in Examples 9to 12 is high in sensitivity to an infrared laser. Furthermore, even ifa non-silicate developing solution was used, a difference in sensitivitybetween two developing solutions having a different dilutedconcentration (from each other) is 20 mJ/cm² or less which ispractically acceptable level, and thus it has been confirmed that theplanographic printing plates are excellent in developing latitude.

Besides, from the results of evaluation of preservation stability, ithas been confirmed that, in all of the planographic printing plates ofthe first embodiment, a fluctuation in the sensitivity between beforeand after preservation is 20 mJ/cm² or less which is practicallyacceptable level. Therefore, the planographic printing plates of thefirst embodiment are evaluated to be excellent in preservation stabilityalso.

From each of Examples mentioned above, it has been found that, when theabove-mentioned specific infrared absorbing agent according to the firstembodiment is used, a photosensitive composition is provided, which ishighly sensitive and excellent in the stability of sensitivity when used(namely, excellent in development latitude) and furthermore is excellentin preservation stability.

Besides, according to a planographic printing plate in which thisphotosensitive composition is used, a direct plate making by using aninfrared laser can be carried out, which is highly sensitive, and isexcellent in development latitude and preservation stability.

As mentioned above, after all, a photosensitive composition of the firstembodiment is wide in development latitude, and is excellent in imageforming properties, and even after the photosensitive composition wasreserved for a long period of time, the image forming properties are notdecreased, and thus it is good in preservation stability. Furthermore,the planographic printing plate in which this photosensitive compositionis used is a positive type of planographic printing plate for directplate making which can form an image through an infrared laser, and thuscan provide the effect of being excellent in image-forming propertiesand preservation stability.

Second Embodiment

Next, a second embodiment of the present invention will be explained indetail.

[Infrared Absorbing Agent(C) Represented by General Formula (II)]

An infrared absorbing agent represented by the above-mentioned generalformula (II) can remarkably lower solubility to an alkaline developingsolution at an image area by the interaction with the above-mentionedpolymer compound (b) which is insoluble in water and soluble in analkaline water. On the other hand, at a non-image area, as alkalinesolubility is recovered by the decomposition of an infrared absorbingagent alone represented by the above-mentioned general formula (II)and/or by the termination of an interaction due to heat generated by theabsorption of near infrared, an excellent discrimination for an imageformation is expressed.

An infrared absorbing agent represented by the above-mentioned generalformula (II) will be more particularly explained.

In the general formula (II), each of X¹ and X² independently represents—CR⁸R⁹—, —S—, —Se—, —NR¹⁰—, —CH═CH— or —O—, wherein each of R⁸ and R⁹represents an alkyl group having 1 to 18 carbon atoms, a substitutedalkyl group having 1 to 18 carbon atoms, an aryl group having 6 to 18carbon atoms, or a substitutional aryl group having 6 to 18 carbonatoms.

“n” represents an integer number of 2 to 4.

Each of R¹ and R² independently represents an alkyl group having 1 to 18carbon atoms, or a substituted alkyl group having 1 to 18 carbon atoms;R³ represents a group selected from the group consisting of an alkylgroup having 1 to 10 carbon atoms, an aryl group, a substitutional arylgroup, a substituted alkyl group having 1 to 10 carbon atoms, and aheterocyclic group having 5 or 6 of carbon in the circle; each of R⁴,R⁵, R⁶ and R⁷ independently represents hydrogen, an alkyl group having 1to 10 carbon atoms, or a substituted alkyl group having 1 to 10 carbonatoms, wherein R⁴ and R⁵, or R⁶ and R⁷ may be bound so as to represent aplurality of atoms necessary for forming an aliphatic 5-membered ring,an aliphatic 6-membered ring, an aromatic 6-membered ring, aromatic10-membered ring, a substitutional aromatic 6-membered ring, or asubstitutional aromatic 10-membered ring; R¹⁰ represents an alkyl grouphaving 1 to 18 carbon atoms, a substituted alkyl group having 1 to 18carbon atoms, an aryl group having 6 to 18 carbon atoms, or asubstitutional aryl group having 6 to 18 carbon atoms.

As an alkyl group for R¹ to R¹⁰ mentioned above, a linear,chain-branching, and ring alkyl groups having 1 to 18 carbon atoms canbe enumerated. Specifically, methyl group, ethyl group, propyl group,butyl group, pentyl group, hexyl group, heptyl group, octyl group, nonylgroup, decyl group, undecyl group, dodecyl group, tridecyl group,hexadecyl group, octadecyl group, eicocyl group, isopropyl group,s-butyl group, t-butyl group, isopentyl group, neopentyl group,1-methylbutyl group, isohexyl group, 2-ethylhexyl group, 2-methylhexylgroup, cyclohexyl group, cyclopentyl group, and 2-norbornyl group can beenumerated. Among others, a linear alkyl group having 1 to 12 carbonatoms, a branched alkyl group having 3 to 12 carbon atoms, and a cyclicalkyl group having 5 to 10 carbon atoms are more preferable.

When these alkyl groups have a substituent, as the substituent, amonovalent non-metallic atomic group, except hydrogen is used. Aspreferable examples, halogen atoms (—F, —Br, —Cl, —I), hydroxyl group,or the like can be enumerated. The examples of these substituent groupsare the same as the substituent groups incorporated into an alkyl group,explained in the first embodiment, and thus an explanation therefor willbe hereupon omitted.

Furthermore, specific examples of an alkyl group incorporated on theabove-described substituent; specific examples of an aryl group; andspecific examples of an alkenyl group are also the same as the onesexplained in the first embodiment mentioned above, and thus anexplanation therefor will be hereupon omitted.

On the other hand, as an alkylene group which constitutes a substitutedalkyl group in combination with a substituent, the one in which any oneof hydrogen atoms on the alkyl group having a carbon number of 1 to 18is removed so as to form a divalent organic residue can be enumerated.Preferably, a linear alkylene group having 1 to 12 carbon atoms, achain-branching alkylene group having 3 to 12 carbon atoms, and a cyclicalkylene group having 5 to 10 carbon atoms can be enumerated. As apreferred specific example of a substituted alkyl group which isobtained by combining the above substituent and the above alkylenegroup, chloromethyl group, bromomethyl group, 2-chloroethyl group or thelike can be enumerated. The preferred concrete example of a substitutedalkyl group which is obtained by combining these substituent groups andthe alkylene groups is the same as those which were explained in thefirst embodiment, and thus an explanation thereof will be hereuponomitted.

As an aryl group in the above-mentioned R¹ to R¹⁰, the one in which acondensed ring is formed from one to three benzene rings; and the one inwhich a condensed ring is formed from a benzene ring(s) and anunsaturated 5-membered ring(s) can be enumerated. As concrete examples,phenyl group, naphthyl group, anthryl group, phenanthryl group, indenylgroup, acetabutenyl group, and fluorenyl group can be enumerated. Amongothers, phenyl group, and naphthyl group are preferred.

As substituent aryl groups, the one which has amonovalent non-metallicatomic group except hydrogen as a substituent on a ring-forming carbonatom of one of the above-mentioned aryl groups is used. As preferredexamples of such substituent groups, the ones enumerated as the alkylgroups, the substituted alkyl groups, or the substituent groups in thesubstituted alkyl groups as mentioned above can be enumerated.

As preferred examples of such substitutional aryl groups, biphenylgroup, tolyl group, xylyl group and the like can be enumerated.Incidentally, preferred examples of these substitutional aryl groups arethe same as the ones explained in the first embodiment, and thus anexplanation therefor will be hereupon omitted.

Q represents a counter ion having a molecular weight of 70 or more,preferably 79 to 500. When the molecular weight of a counter ion Q isless than 70, the probability of causing the following various problemsbecomes higher, and thus such a lowmolecular weight is not preferred:that the volatilization of an acid resulting from the decomposition of acolorants, the existence of impurities or the like is caused, andthereby the stability of an infrared absorbing agent itself isdecreased; that the image-forming properties of a photosensitivematerial is deteriorated as time goes; that the organicitiy of theinfrared absorbing agent itself is decreased and thereby the solubilityto a coating liquid becomes insufficient; and that by the decreasing ofthe organicity, the affinity with an alkaline-water soluble polymercompound or the other compound in a photosensitive layer is decreasedand the coagulation of a coloring occurs, thereby deteriorating theimage-forming properties.

As the counter ions, the ones as represented by the general formula(III) are preferred, wherein A represents an atom selected from thegroup consisting of B, P, As, Sb, Cl and Br. From the viewpoint of easein synthesis, and safety of the compound, B, P, Sb and Cl are preferred.

Y represents a halogen atom such as Cl, I, Br, F, or oxygen atom. Amongothers, from the viewpoint of ease in obtaining a raw material, Y ispreferably fluorine or oxygen atom.

m represents an integer of 1 to 6, preferably 4 to 6.

Furthermore, as Q, the one having a sulfonic acid structure in itsstructure is also preferably used. No matter what structure Q has, it isrequired that the molecular weight of the counter ion Q alone is 70 ormore.

Additionally, concrete examples of preferred counter ions (such as ClO₄⁻, BrO₄ ⁻) in the second embodiment, and concrete examples of counteranions (such as methanesulfonate) having a sulfonic acid structure,which can be used as a counter ion Q in an infrared absorbing agent inthe second embodiment are the same as the ones explained in the firstembodiment, and thus an explanation therefor will be hereupon omitted.

Hereinafter, a process for preparing an infrared absorbing agent asrepresented by the general formula (II) mentioned above will beexplained.

An infrared absorbing agent as represented by the above general formula(II) can be prepared according to a publicly known organic synthesistechnology. As concrete synthetic processes, the ones disclosed in J.Org. Chem. (Journal of Organic Chemistry), Vol. 57 (No. 17), 1992,p.4578-4580; and Registered U.S. Pat. No. 2758136 can be enumerated.

Concrete examples of infrared absorbing agents as represented by theabove general formula (II) are enumerated as follows. However, infraredabsorbing agents in the second embodiment are not intended to be limitedto these concrete examples.

In the second embodiment, these infrared absorbing agents can be addedthereto in a ratio of 0.01 to 50% by weight, preferably 0.1% to 20% byweight, more preferably 0.5% to 15% by weight to the whole solids of aphotosensitive composition. When the added amount is less than 0.01% byweight, an image can not be formed by using the photosensitivecomposition. On the other hand, when the amount is more than 50% byweight and it is used as a photosensitive layer in a planographicprinting plate, a stain may be caused at a non-image area.

To the photosensitive composition in the second embodiment, otherpigments or dyes having infrared absorbing properties can be added aswell as the present infrared absorbing agents, in order to improveimage-forming properties.

As pigments, commercial pigments; and pigments disclosed in Color Index(C. I.) Handbook, “New Pigments Handbook” (Edit. by Japan PigmentsTechnical Society, 1977), “New Pigments Application Technology” (Pub. byCMC, 1986), and “Printing Ink Technology” (Pub. by CMC, 1984) areavailable.

Further, the types of pigments (such as a black pigment, a yellowpigment, an orange pigment, carbon black); the surface treatment ofpigments; the particle sizes of pigments; method for dispersingpigments; examples of dyes; the manner of adding pigments and/or dyes;and the like are the same as the ones enumerated in the first embodimentmentioned before, and thus a detailed explanation thereon will behereupon omitted.

Besides, with respect to aqueous alkaline solution soluble resins(polymer compounds) (b) as used in the second embodiment, the sameaqueous alkaline solution soluble resins as the ones used in the firstembodiment are wholly used, including characteristics such as preferredacid radicals, namely (b-1) phenolichydroxidegroup, (b-2)sulfoneamidegroup, and (b-3) active imide group.

Furthermore, in the same manner as the first embodiment, othercomponents including an onium salt, a counter ion of the onium salt, aburning agent, an image coloring agent, a surfactant may be suitablyadded thereto. These components are the same as the ones explained inthe first embodiment, and thus an explanation thereon will be hereuponomitted.

Besides, with respect to substrates used in the second embodiment, theconstitution and a method of producing the same are the same as the onesexplained in the first embodiment, and thus an explanation thereon willbe hereupon omitted.

Furthermore, an image exposure, a developing treatment and the othertreatments to a photosensitive planographic printing plate in which aphotosensitive composition of the second embodiment is used are the sameas the ones explained in the first embodiment, and thus an explanationthereon will be hereupon omitted.

Hereinafter, the second embodiment will be explained according toExamples. However, the scope of the second embodiment is not intended tobe limited by these Examples.

Examples 1 to 4

[Preparation of Substrates]

An aluminum plate (Material: 1050) having a thickness of 0.3 mm waswashed and degreased with trichloroethylene, and thereafter this surfacewas subjected to graining by using a nylon brush and a 400 meshpumice/water suspension, and then cleanly washed with water. This platewas immersed into an aqueous solution of 25% of sodium hydroxide at atemperature of 45° C. for a period of 9 seconds so as to etch the plate.After water-washed, and the plate was furthermore immersed into a 20%nitrous acid for a period of 20 seconds, and water-washed, wherein theetched amount on the surface by graining was about 3 g/m². Then, thisplate was anodized by a direct current at a current density of 15 A/dm²in an amount of 3 g/m² using a 7% sulfuric acid as an electrolyte so asto form an anodized film thereupon, and thereafter water-washed, anddried so as to obtain substrates A. The following primer coating liquidwas applied to the substrates A, and the consequent films were dried ata temperature of 90° C. for a period of one minute so as to obtainsubstrates B. The applied amount of the films after drying was 10 mg/m².

<Composition of Primer Coating Liquid> β-alanine 0.5 g Methanol 95 gWater 5 g

The following photosensitive liquids 1 in which infrared absorbingagents are varied as shown in the following Table 1 were prepared, andeach of the photosensitive liquids 1 was applied to the resultantsubstrate above so as to obtain an applied amount of 1.8 g/m², and thusplanographic printing plates for Examples 1 to 5 were provided.

<Composition of Photosensitive Liquids 1> m, p-cresolnovolak 1.0 g (m/pratio = 6/4; weight average molecular weight = 3500; with 0.5% by weightof non-reacted cresol) (alkaline water soluble polymer compound)Infrared absorbing agents as described 0.2 g in Table 3 (compoundsrepresented by the general formula (II)) Dye in which a counter anion of0.02 g victoria-pure-blue BOH is replaced with 1-naphthalenesulfonicacid anion Fluorine-contained surfactant 0.05 g (MEGAFAC F-177;manufactured by DAINIPPON INK AND CHEMICALS, INC.) γ-Butyrolactone 3 gMethylethyl ketone 8 g 1-Methoxy-2-propanol 7 g

Comparative Examples 1 to 2

Planographic printing plates in Comparative Examples 1 to 2 wereprepared in the substantially same manner as the one in Example 1,except that infrared absorbing agents as represented by the generalformula (II) incorporated into photosensitive liquids 1 were replacedwith an infrared absorbing agent B-1 or B-2 as represented by thefollowing structures.

Examples 6 to 10

<Example of Synthesis (Copolymer 1)>

31.0 g (0.36 moles) of methacrylic acid, 39.1 g (0.36 moles) of ethylchloroformate and 200 ml of acetonitrile were introduced into a threeneck flask of 500 ml as provided with a stirrer, a condenser tube and adropping funnel, and the mixture was stirred, while the mixture wascooled on an ice bath. Into the mixture, 36.4 g (0.36 moles) oftriethylamine was the dropping was finished, the ice bath was removed,and the mixture was stirred at a room temperature for a period of 30minutes.

To this reactant mixture, 51.7 g (0.30 moles) ofp-aminobenzensulfonamide was added, and the mixture was stirred for aperiod of one hour, while heating at a temperature of 70° C. with an oilbath. After the reaction was finished, this mixture was added to oneliter of water, while the water was stirred, and the consequent mixturewas stirred for a period of 30 minutes. The mixture was filtrated toseparate a deposit, this deposit was slurried with 500 ml of water, andthereafter this slurry was filtrated, and the obtained solids were driedso as to obtain a white solid of N-(p-aminosulfonylphenyl)methacrylamide (with a yield of 46.9 g).

Next, 4.61 g (0.0192 moles) of N-(p-aminosulfonylphenyl)methacrylamide,2.94 g (0.0258 moles) of ethyl methacrylate, 0.80 g (0.015 moles) ofacrylonitrile and 20 g of N,N-dimethylacetamide were introduced into athree neck flask of 20 ml as provided with a stirrer, a condenser tubeand a dropping funnel, and the mixture was stirred, while the mixturewas heated at a temperature of 65° C. on a hot water bath. Into themixture, 0.15 g of “V-65” (manufactured by Wako Pure ChemicalIndustries, Ltd.) was added, and the mixture was stirred for 2 hoursunder a nitrogen flow, while a temperature of 65° C. was maintained. Tothis reactant mixture, a blend of 4.61 g ofN-(p-aminosulfonylphenyl)methacrylamide, 2.94 g of ethyl methacrylate,0.80 g of acrylonitrile, N,N-dimethylacetamide and 0.15 g of “V-65” wasdropped through the dropping funnel over two hours. After the droppingwas finished, the consequent mixture was furthermore stirred at atemperature of 65° C. for a period of two hours. After the reaction wasfinished, 40 g of methanol was added to the mixture, cooled, and theconsequent mixture was added to 2 litters of water, while the water wasstirred. After the mixture was stirred for a period of 30 minutes, adeposit was filtered out, separated and dried so as to obtain 15 g of awhite solid. A gel permeation chromatography was used to determine ofthe weight average molecular weight (on the base of polystyrene) of thiscopolymer 1. As a result, the weight average molecular weight was53,000.

The following photosensitive liquids 2 in which infrared absorbingagents are varied as shown in the following Table 3 were prepared, andeach of the photosensitive liquids 2 was applied to the same substrateas the one used in Examples 1 to 4, so as to obtain an applied amount of1.8 g/m², and thus planographic printing plates for Examples 6 to 10were provided.

<Composition of Photosensitive Liquids 2> The above-mentioned copolymer1 0.75 g (alkaline water soluble polymer compound) m, p-cresolnovolak0.25 g (m/p ratio = 6/4; weight average molecular weight = 3500; with0.5% by weight of non-reacted cresol) (alkaline water soluble polymercompound) Tetrahydrophthalic anhydride 0.03 g Infrared absorbing agentsas described 0.017 g in Table 3 (compounds represented by the generalformula (II)) Dye in which a counter anion of 0.015 g victoria-pure-blueBOH is converted into 1-naphthalenesulfonic acid anionFluorine-contained surfactant 0.05 g (MEGAFAC F-177; manufactured byDAINIPPON INK AND CHEMICALS, INC.) γ-Butyrolactone 10 g Methylethylketone 10 g 1-Methoxy-2-propanol 1 g

Comparative Examples 3 and 4

Planographic printing plates in Comparative Examples 3 and 4 wereprepared in the substantially same manner as the one in Example 6,except that infrared absorbing agents as represented by the generalformula (II) incorporated into photosensitive liquids 2 were replacedwith an infrared absorbing agent B-1 or B-2 as represented by theabove-mentioned structure.

[Performance Evaluation of Planographic Printing Plate]

On each of the planographic printing plates in Examples 1 to 10 andComparative Examples 1 to 4, which were produced as mentioned above,performance evaluation was made according to the following criteria. Theresults of evaluation are shown in Table 3.

Image Forming Properties: Evaluation of Sensitivity and DevelopmentLatitude

The consequent planographic printing plates were exposed by using asemiconductor laser having a wave length of 840 nm, and developed byusing an automatic processor (manufactured by Fuji Photo Film Co., Ltd.“PS processor 900VR”) in which developing solution DP-4 and rinse liquidFR-3 (1:7) (manufactured by Fuji Photo Film Co., Ltd.) were charged,wherein DP-4 was used at dilution ratios of two levels of 1:6 and 1:12.The width of line at a non-image area as obtained with each developingsolution was determined, and a radiation energy of a laser correspondingto the line width was determined, which was used as sensitivity. Then,differences between what was diluted at a ratio of 1:6 which is thestandard and what was diluted at a ratio of 1:12 were recorded. Thesmaller the differences are, the better the development latitude is, andthe value of 20 mJ/cm² or less represents a practically acceptablelevel.

Evaluation of Preservation Stability

The consequent planographic printing plates were preserved at atemperature of 60° C. for a period of 3 days prior to the exposure to alaser, and thereafter a laser exposure and a development were carriedout in the same manner as the one mentioned above, and a sensitivity wasdetermined in the same manner so as to compare the new results with theaforementioned results. When the fluctuation of sensitivity is 20 mJ/cm²or less, preservation stability was evaluated to be excellent and less,preservation stability was evaluated to be excellent and to be on apractically acceptable level.

TABLE 3 Development Infrared Sensitivity Latitude Preservation AbsorbingAgent (mJ · cm²) (mJ · cm²) Stability Example 1 IR-32 125 10 GoodExample 2 IR-37 120 15 Good Example 3 IR-44 125 15 Good Example 4 IR-49120 15 Good Example 5 IR-55 120 10 Good Example 6 IR-32 115 5 GoodExample 7 IR-37 115 10 Good Example 8 IR-44 110 10 Good Example 9 IR-49115 5 Good Example 10 IR-55 115 5 Good Comparative B-1 145 25 Badexample 1 Comparative B-2 140 20 Bad a little example 2 Comparative B-1135 25 Bad example 3 Comparative 8-2 130 20 Bad a little example 4

From the results shown in Table 3, it is found that, as compared withplanographic printing plates in Comparative Examples 1 to 4 in which aninfrared absorbing agent B-1 not having at the methyne chain an —S—connecting substituent, or an infrared absorbing agent B-2 having at themethyne chain an —S— connecting substituent but the molecular weight ofa counter plates in Examples 1 to 10 is high in sensitivity to aninfrared laser. Furthermore, in each of planographic printing plates ofExamples 1 to 10, a difference in sensitivity between two developingsolutions having a different diluted concentration from each other is 20mJ/cm² or less which is practically acceptable level (which is a levelwhich does not present any problems in actual practice). Accordingly,and thus it has been confirmed that the planographic printing plates areexcellent in developing latitude.

Besides, from the results of evaluation of preservation stability, ithas been confirmed that, in all of the planographic printing plates ofthe second embodiment, a fluctuation in the sensitivity between beforeand after preservation is 20 mJ/cm² or less which is a practicallyacceptable level. Therefore, the planographic printing plates ofembodiments of the present invention were evaluated to be also excellentin preservation stability.

Examples 11 to 15

The substrate A used in Example 6 was treated with an aqueous solutionof 2.5% by weight of sodium silicate at a temperature of 30° C. for aperiod of 10 seconds, and coated with the following primer coatingliquid, and the film was dried at a temperature of 90° C. for a periodof one minute so as to obtain a substrate C. The applied amount of thefilm layer after drying was 15 mg/m².

<Composition of Primer Coating Liquid> Following copolymer having  0.3 ga molecular weight of 28000 Methanol 100 g Water  1 g

Molecular Weight 28,000

The same photosensitive liquids 1 as the ones used in theabove-mentioned Examples 6 to 10 were applied to the consequentsubstrates C so that an applied amount was 1.8 g/m², to obtainplanographic printing plates for Examples 11 to 15.

Each of the consequent planographic printing plates in Examples 10 to 15was exposed at a main scanning speed of 5 m/second by using asemiconductor laser having an output of 500 mW, a wave length of 830 nmand a beam diameter of 17 μm (1/e²) and thereafter developed by using anautomatic processor “PS processor 900VR” (manufactured by Fuji PhotoFilm Co., Ltd.) into which two developing solutions (namely, adeveloping solution 1 and a developing solution 2) each having adifferent dilution ratio and the following composition as shown belowand a rinsing liquid FR-3 (which is diluted at a ratio of 1:7) werecharged. Then sensitivities and development latitudes thereof wererecorded. Furthermore, the evaluation of preservation stability was madein the same manner as the one in Examples 1 to 10.

The results are shown in Table 4.

TABLE 4 <Developing Solution 1> D-sorbitol 5.1 parts by weight Sodiumhydroxide 1.1 parts by weight Triethanolamine, 0.03 parts by weightethylene oxide additives (30 moles) Water 93.9 parts by weight<Developing Solution 2> D-sorbitol 5.1 parts by weight Sodium hydroxide1.1 parts by weight Triethanolamine, 0.03 parts by weight ethylene oxideadditives (30 moles) Water 140.7 parts by weight Development InfraredSensitivity Latitude Preservation Absorbing Agent (mJ · cm²) (mJ · cm²)Stability Example 11 IR-32 120 10 Good Example 12 IR-37 115 10 GoodExample 13 IR-44 110 10 Good Example 14 IR-49 115  5 Good Example 15IR-55 115 10 Good Comparative B-1 140 20 Slightly Bad example 5Comparative B-2 135 20 Slightly Bad example 6

From the results shown in Table 4, it is found that, as Example 5 or 6in which an infrared absorbing agent B-1 not having at the methyne chainan —S— connecting substituent, or an infrared absorbing agent B-2 havingat the methyne chain an —S— connecting substituent but the molecularweight of a counter ion being less than 70 is used, each of planographicprinting plates in Examples 11 to 15 is high in sensitivity to aninfrared laser. Furthermore, even if a non-silicate developing solutionwas used, a difference in sensitivity between two developing solutionshaving a different diluted concentration is 20 mJ/cm² or less which is apractically acceptable level, and thus it has been confirmed that theplanographic printing plates are excellent in developing latitude.

Besides, from the results of evaluation of preservation stability, ithas been confirmed that, in all of the planographic printing plates ofthe second embodiment, a fluctuation in the sensitivity between beforeand after preservation is 20 mJ/cm² or less which is a practicallyacceptable level. Therefore, the planographic printing plates of thefirst embodiment are evaluated to be also excellent in preservationstability.

From each of Examples mentioned above, it has been found that when theabove-mentioned specific infrared absorbing agent according to thesecond embodiment is used, a photosensitive composition can be provided,which is excellent in the stability of sensitivity when developingsolutions of different concentrations are used (namely, excellent indevelopment latitude) and furthermore is excellent in preservationstability.

Besides, according to a planographic printing plate in which thisphotosensitive composition is used, a direct plate making by using aninfrared laser can be carried out, which is highly sensitive, and isexcellent in development latitude and preservation stability.

As mentioned above, after all, a photosensitive composition of thepresent invention is wide in development latitude, and is excellent inimage forming properties, and even after the photosensitive compositionwas reserved for a long period of time, the image forming properties arenot decreased and thus it is good in preservation stability.Furthermore, the planographic printing plate in which thisphotosensitive composition is used is a positive type of planographicprinting plate for direct plate making which can form an image throughan infrared laser, and thus can provide the effect that it is excellentin image forming properties and preservation stability.

What is claimed is:
 1. A photosensitive composition comprising: (a) aninfrared absorbing agent represented by the following formula (II); and(b) a polymer compound which is insoluble in water and soluble in anaqueous alkali solution, wherein; the solubility of the photosensitivecomposition in an aqueous alkali solution is changed by radiation of aninfrared laser;

wherein X¹ and X² independently represent —CR⁸R⁹—, —S—, —Se—, —NR¹⁰—,—CH═CH— or —O—, n denotes an integer of 2, 3 or 4, R¹ and R²independently represent an alkyl group having 1 to 18 carbon atoms, R³represents a group selected from the group consisting of an alkyl grouphaving 1 to 10 carbon atoms, a substituted alkyl group having 1 to 10carbon atoms, an aryl group, a substituted aryl group and a heterocyclicgroup having 5 to 6 carbon atoms in the ring, R⁴, R⁵, R⁶ and R⁷independently represent a hydrogen atom, an alkyl group having 1 to 10carbon atoms or a substituted alkyl group having 1 to 10 carbon atomsand may represent a plurality of atoms required for R⁴ and R⁵ or R⁶ andR⁷ to be combined with each other to form an aliphatic 5- or 6-memberedring, an aromatic 6-membered ring, an aromatic 10-membered ring, asubstituted aromatic 6-membered ring or a substituted aromatic10-membered ring, R⁸ and R⁹ independently represent an alkyl grouphaving 1 to 18 carbon atoms, a substituted alkyl group having 1 to 18carbon atoms, an aryl group having 6 to 18 carbon atoms or a substitutedaryl group having 6 to 18 carbon atoms, R¹⁰ represents an alkyl grouphaving 1 to 18 carbon atoms, a substituted alkyl group having 1 to 18carbon atoms, an aryl group having 6 to 18 carbon atoms or a substitutedaryl group having 6 to 18 carbon atoms and Q represents a counter ionhaving a molecular weight of 70 or more.
 2. A photosensitive compositionaccording to claim 1, wherein the counter ion Q of the infraredabsorbing agent represented by said formula (II) is represented by thefollowing formula (III), [A—(Y)_(m)]^(⊖)  (III) wherein A represents anatom selected from the group consisting of B, P, As, Sb, Cl and Br, Yrepresents a halogen atom or an oxygen atom and m denotes an integerfrom 1 to
 6. 3. A photosensitive composition according to claim 2,wherein said counter ion Q has a molecular weight of 79 to
 500. 4. Aphotosensitive composition according to claim 1, wherein the counter ionQ of the infrared absorbing agent represented by said formula (II) is acounter ion having a sulfonic acid structure.
 5. A photosensitivecomposition according to claim 1, wherein said aqueous alkalisolution-soluble polymer compound has an acid group structure on theprincipal chain or side chain thereof.
 6. A photosensitive compositionaccording to claim 5, wherein said acid group structure includes aphenolic hydroxyl group, a sulfoneamide group and an activated imidegroup.
 7. A photosensitive composition according to claim 1, wherein theinfrared absorbing agent is added in a proportion of 0.01 to 50% byweight based on the total solid of the photosensitive composition.
 8. Aplanographic printing plate comprising disposing a photosensitive layerconsisting of the photosensitive composition as claimed in claim 1 on asubstrate.
 9. A photosensitive composition comprising: (a) an infraredabsorbing agent represented by the following formula (II); and (b) apolymer compound which is insoluble in water and soluble in an aqueousalkali solution, wherein; the solubility of the photosensitivecomposition in an aqueous alkali solution is changed by radiation of aninfrared laser;

wherein X¹ and X² independently represent —CR⁸R⁹—, —S—, —Se—, —NR¹⁰—,—CH═CH— or —O—, n denotes an integer of 2, 3 or 4, R¹ and R²independently represent an alkyl group having 1 to 18 carbon atoms or asubstituted alkyl group having 1 to 18 carbon atoms, R³ represents asubstituted aryl group, R⁴, R⁵, R⁶ and R⁷ independently represent ahydrogen atom, an alkyl group having 1 to 10 carbon atoms or asubstituted alkyl group having 1 to 10 carbon atoms and may represent aplurality of atoms required for R⁴ and R⁵ or R⁶ and R⁷ to be combinedwith each other to form an aliphatic 5- or 6-membered ring, an aromatic6-membered ring, an aromatic 10-membered ring, a substituted aromatic6-membered ring or a substituted aromatic 10-membered ring, R⁸ and R⁹independently represent an alkyl group having 1 to 18 carbon atoms, asubstituted alkyl group having 1 to 18 carbon atoms, an aryl grouphaving 6 to 18 carbon atoms or a substituted aryl group having 6 to 18carbon atoms, R¹⁰ represents an alkyl group having 1 to 18 carbon atoms,a substituted alkyl group having 1 to 18 carbon atoms, an aryl grouphaving 6 to 18 carbon atoms or a substituted aryl group having 6 to 18carbon atoms and Q represents a counter ion having a molecular weight of70 or more.
 10. A photosensitive composition comprising: (a) an infraredabsorbing agent represented by the following formula (II); and (b) apolymer compound which is insoluble in water and soluble in an aqueousalkali solution, wherein; the solubility of the photosensitivecomposition in an aqueous alkali solution is changed by radiation of aninfrared laser;

wherein X¹ and X² independently represent —CR⁸R⁹—, —S—, —Se—, —NR¹⁰—,—CH═CH— or —O—, n denotes an integer of 2, 3 or 4, R¹ and R²independently represent an alkyl group having 1 to 18 carbon atoms or asubstituted alkyl group having 1 to 18 carbon atoms, R³ represents aheterocyclic group having 5 to 6 carbon atoms in the ring, R⁴, R⁵, R⁶and R⁷ independently represent a hydrogen atom, an alkyl group having 1to 10 carbon atoms or a substituted alkyl group having 1 to 10 carbonatoms and may represent a plurality of atoms required for R⁴ and R⁵ orR⁶ and R⁷ to be combined with each other to form an aliphatic 5- or6-membered ring, an aromatic 6-membered ring, an aromatic 10-memberedring, a substituted aromatic 6-membered ring or a substituted aromatic10-membered ring, R⁸ and R⁹ independently represent an alkyl grouphaving 1 to 18 carbon atoms, a substituted alkyl group having 1 to 18carbon atoms, an aryl group having 6 to 18 carbon atoms or a substitutedaryl group having 6 to 18 carbon atoms, R¹⁰ represents an alkyl grouphaving 1 to 18 carbon atoms, a substituted alkyl group having 1 to 18carbon atoms, an aryl group having 6 to 18 carbon atoms or a substitutedaryl group having 6 to 18 carbon atoms and Q represents a counter ionhaving a molecular weight of 70 or more.
 11. A photosensitivecomposition comprising: (a) an infrared absorbing agent represented bythe following formula (II); and (b) a polymer compound which isinsoluble in water and soluble in an aqueous alkali solution, wherein;the solubility of the photosensitive composition in an aqueous alkalisolution is changed by radiation of an infrared laser;

wherein X¹ and X² independently represent —CR⁸R⁹—, —S—, —Se—, —NR¹⁰—,—CH═CH— or —O—, n denotes an integer of 2, 3 or 4, R¹ and R²independently represent an alkyl group having 1 to 18 carbon atoms or asubstituted alkyl group having 1 to 18 carbon atoms, R³ represents agroup selected from the group consisting of an alkyl group having 1 to10 carbon atoms and a substituted alkyl group having 1 to 10 carbonatoms, R⁴, R⁵, R⁶ and R⁷ independently represent a hydrogen atom, analkyl group having 1 to 10 carbon atoms or a substituted alkyl grouphaving 1 to 10 carbon atoms and may represent a plurality of atomsrequired for R⁴ and R⁵ or R⁶ and R⁷ to be combined with each other toform an aliphatic 5- or 6-membered ring, an aromatic 6-membered ring, anaromatic 10-membered ring, a substituted aromatic 6-membered ring or asubstituted aromatic 10-membered ring, R⁸ and R⁹ independently representan alkyl group having 1 to 18 carbon atoms, a substituted alkyl grouphaving 1 to 18 carbon atoms, an aryl group having 6 to 18 carbon atomsor a substituted aryl group having 6 to 18 carbon atoms, R¹⁰ representsan alkyl group having 1 to 18 carbon atoms, a substituted alkyl grouphaving 1 to 18 carbon atoms, an aryl group having 6 to 18 carbon atomsor a substituted aryl group having 6 to 18 carbon atoms and Q representsa counter ion having a molecular weight of 70 or more.